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The first question is a little more broad and I'm not going to go into detail on specific combos but I will say that in my view, having the right abilities available for the content you're trying to clear is generally more important than pairing specific jobs.
For example, if you're trying to clear a particularly difficult boss fight, you might want one character as a primary breaker/damage-dealer (most likely a Scholar for a good chunk of the game), someone with the Leghold Trap ability from the Hunter job (and break potential if there's a bow weakness), a Cleric with their divine ability to boost your damage-dealer (if possible) and heal as needed, and whatever else makes sense for the fight in question and the weaknesses involved. Basically, whatever keeps the shield-breaking/damage machine rolling without your damage-dealer(s) having to waste their own turns healing/buffing/debuffing instead of attacking.
And as a side-note, exploring and finding the best equipment available (many of the best/second-best pieces of gear in the game are surprisingly easy to get a hold of shortly after starting the game) will make a far bigger difference in your overall power than your job-selections or subjob-stats in most of the early/mid-game content.
Honestly, there's only one specific late-game job pairing with Tressa that I'd say is hard to ignore because of a uniquely overpowered interaction with the abilities in those two classes. but otherwise, it's more a matter of bringing the right tools for the job than finding the 'correct' pairs for all content.
I would say in Octopath, some Path Actions and Talent are very strong. What you can get with Purchase/Steal can be insanely good if you know where and how to get some of the stuff. Some purple locked chest also have extremely good stuff in some of them. The ability to find money with Tressa just by walking around is a pretty nice perk as well. For all those reasons I like a lot having Tressa and Therion in my main party. Also I like a lot having Cyrus talent to reveil weaknesses so that's another character I like a lot to start with.
Tressa/Scholar in my opinion is probably the very best combination early on I would say If you know how to find the Rune Glaive spear and other good elemental gear.
Cyrus without any job is almost as good as Tressa. The scholar job alone is just very good with the right equipment. I usually like to equip the Thief job on Cyrus just for the utility of stealing mana.
With Therion the job I chose highly depends where I fight. In the tomb of kings I like using the Warrior job on him as every single monsters in there are weak to sword so level slash ability can be nice in there. At level 18-20 I usually go fight in Maw of the Ice Dragon and I like the hunter job in there again for the purpose of breaking enemies.
Early game my 4th character I picked is usually H'aanit, just because she's the best character to break enemies in Maw of the Ice Dragon and I usually give her Apothecary job just because there's a very powerful axe you can get in a chest, but for a new players who don't really know where to fight and how to cheese the game you're probably better playing with Ophilia who is best at healing your party. With Ophilia anything can be good but I would tend to think she can be a nice buffer with the dancer job.
Late game you'll have access to 4 advance job if you can beat the bosses guarding them. All 4 of them are extremely powerfull Sorcerer, Starseer, Runeblade, Warmaster.
My personal favorite to equip the Sorcerer is Therion because sorcerer spells cost a lot but Therion is the best to refill his mana pool.
Tressa is probably the best character to use the Runeblade job because of her sidestep ability that you can shared with the whole party instead of being only single target without the job and she has good affinity with elemental damage which is good with the runeblade.
Both Olberic and H'aanit are pretty good at handling the Warmaster job, just because they both have high physical strength.
As for the Starseer, the job itself is amazing for the support skill (passive) you can learn but other than that I usually don't use that job very much.