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Unique items, essentially the closest thing to "Legendary" status, will hardly ever drop in the first couple of acts. It seems that once you hit part 2 (Acts 6-10) the drop rate does increase. Some of these items will change the way a certain build is played and their are some builds that require these items to even come close to functioning. There will be some builds, especially in late-game, that will require these kinds of items.
I by no means would call myself an expert in this game, but you always want to look out for items that have linked sockets. These will allow support gems to function. Especially when leveling try to keep your elemental resistances high, and especially for melee make sure you have plenty of health. If you have any further questions I'm always willing to help.
Most speed runners use crafting leveling recipes (you can find them on the wiki), that give you stuff with meaningful mods (like +1 to skills, increased damage, movement speed etc.).
Something that will make your life easier : a blue item with 2 good mods and useful sockets is always better than 90% of the trash rares you find, and sockets matter, a lot (support gems are the backbone of you build's damage, you can't do much withtout a good gem setup, doesn't matter how much passives you get or good items you have, gems do most of the work because of their multipliers).
Then lategame (in areas lv80+, because before that you can't get the best mods on items), this is going to change a bit, what people want are good rares, usually tri resists + life and all the links you can get with perfect or near perfect rolls. On the weapon they want mods corresponding to the build (so matching elemental flat and increased damage, cast of attack speed, crit if they're crit etc.).
Some uniques are valuables if they are build enablers, but for most builds, a perfect rolled rare will do way better than any unique.
Between leveling and high endgame you'll be in that strange zone where you'll do recipes for currency (mostly regals, jewelers, chromatics, sometimes chaos), and you'll only pick rares, 6 socket items, or RGB linked items (and gems with quality on them) just to vendor and get orbs.
About rare picking (usually for recipes), since there is no gold, an item is valuable depending on it's size in the inventory. Never pick 2H items, too much space, prefer daggers or claws. Don't pick body armors unless you need to store some for recipes. If you're looking for stuff to equip, take it, id and drop it if it's not useful, it's not gonna sell anyway, and scrolls are cheap, especially lategame.
Anyway at low levels the only thing you care about is the number of linked gem slots on an item and some resistances. There are also leveling recipes to craft some pretty useful leveling gear. At this stage of a league you can also buy most low level rares and uniques for an alch or 2 on poe.trade
P.S I would advise you to follow a good 3.0 starter build guide unless you really want to have to reroll once your current character hits a brick wall well before end game when those OP uniques , rares and high tier currency start dropping.
The loot/item system in PoE is actually quite varied and well thought-out but it takes some getting used to. Your best bet for now is to get an item filter and devote some 2-3 hours to reading guides - especially the ones about the use and value or differet orbs and vendor recipes, as it's the easiest way to get the ball rolling when you first start. Act 2 is the top of the tip of an iceberg conent- and loot-wise.
There are indeed game-changing uniques that instead of (or in addition to) having godly stats can alter the way the character plays - some of them have the impact comparable to the so-called keystone passives (for reference, check "Chaos Inoculation" or "Blood Magic" - it'll give you the idea what we're talking about here), or even outright grant those without the need to invest in the skill tree. But that's something to worry about when you're further into the game.
High-level rare items (yellow ones) can be some of the (if not THE) most powerful ones in the game, but for that you have to have just the right combination of random properties - something that I honestly don't think is worth your time getting into right now as you will be switching items very often while leveling.
Speaking of currency, the most important advice I can give a newbie: SPEND YOUR CURRENCY SPARINGLY on modifying the items that you use. The game is somewhat misleading in making you believe that you can easily craft your own gear - truth is, there is so much randomness involved that you can spend A LOT and still not get the socket number/color/link combination that you want. If you want to upgrade your gear you're better off gathering some "base" currency (orbs of alteration, chromatic orbs) in bulk, then exchaning it for "trading" currency (rough guideline: alchemy is the currency used for trading cheap stuff, chaos for the regular stuff, exalted for the top-notch stuff) and using that to buy the items that others are selling.
Only use currency to slightly improve the gear that is close to what you need already. Learn about the socket colors and their relation to the item's stat requirements and (for now) NEVER try to 6-socket or 6-link an item - it's a gamble where the house always wins.
The exception are the blacksmith/armorer orbs, which are common and useful to improve quality of the items that you're gonna be using for a couple of levels.
In-game trading is a rather cumbersome joke and waste of time unless your idea of fun is spamming and scamming people. Familiarize yourself with poe.trade and currency.poe.trade in order to sell and acquire gear
Back to your original question: you should mostly be picking up items that you can turn into currency (orbs) via the vendor recipe system. As anything in PoE the rabbit hole goes rather deep, but to begin with I'd advice:
1. Get yourself an up-to-date item filter. Speed and efficiency are key to earing currency in PoE, with the high amount of items that drop you really need to minimize the time that you spend looking through the loot on the ground.
2. I'd advise against picking up large (2x4) items - they are not inherently more valuable than smaller ones and clog up your inventory in a hurry - you don't want to spend too much time running back and forth to vendor your booty.
3. Items with 6 sockets - each one gets you a couple jewellers orbs. Depending on the base item type they might be worth selling on the player market. If you find a 6-socket 6-link item DEFINITELY check it's going price, they're exceedingly rare and possible very valuable.
4. Rare (yellow) items - identify them before selling to vendor to get shards that combine into various valuable orbs (most commonly alteration, which are the easiest to gather in bulk and exchange for chaos)
5. Items with 3 linked sockets, each of different color - sell them for chromatic orbs, always in high demand.
6. Small/medium items with quality on them - they can be sold (in bulk - you need to have 40% of combines quality) for various quality-boosting orbs. Keep an eye out for quality skill gems and flasks especially, best size-to-value ratio of the bunch.
7. Small magic (blue) items - sell them without identifying. Very low priority comparede to the ones mentioned before.
Holy crap, though. Vendor recipies. This is a whole aspect of the game I had no idea about until this thread. This is probably just a case of a new player feeling overwhelmed, but it seems overly complex.
So vendors aren't really for selling items to get (what I thought were random) currency items so much as they are a crafting system to get specific items, such as gear and other currency.