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Now, if you are talking about elemental attacks, they already exist. Like static strike, ice shot, wildstrike, infernal blow, molten strike etc.
If you want to use spells in conjunction with attacks, you best bet is a cast ton crit build, where you use attack skills that cast spells when you crit. Usually you use a pure crit build for those.
http://pathofexile.gamepedia.com/Crown_of_Eyes
You could try making a Blade Flurry supported by Cast while Channelling + spell gem. (Cast the linked spell every 0.35 seconds). You would only focus on getting +spell damage and the helmet would transfer that damage to Blade Flurry (Attack)
EDIT:
Emberwake + The Taming rings (+3000% increased dmg if you can get 300 ignites)
Blade Flurry + CwC + Bladefall? + Concentrated Effect + Chance to Ignite + Added Fire
Witch - Elementalist for Beacon of Ruin (Spread ignites to other enemies)
Focus passive tree on defense and ignite chance. ES%, CI, ignite%, Vaal Pact, jewels.
This coming off the top of my head. No idea how well it would actually work. But thats my take on a attack+spell build.
Damage probably on the lower end without any MORE multiplier%s and ignites will probably never reach 300 stacks.
Also, I think Chieftain bonuses outweigh the small damage bonus from Berserker for Ancestral Warchief.
Chieftain does not have enough dps to take down major bosses unless you have best in slot gear. Then maybe with insane gear I would consider chieftain over berserker for aw totems right now.
Once you start killing everything in sight with 1 hit, you stop thinking about how to improve DPS and start looking at survival. Thats where Chieftan shines and Berserker fails.
I tested both classes with Facebreakers, Disfavour Bleed/poison and Rare 2h Axe. I prefer Chieftan. (SS in my library)
Sorry OP for the off topic. Hope you find a build you like.
A properly geared facebreaker zerker has 2million dps.
And thats 550k x3 (3 totems = 1,650,000dps) While in hideout. Chieftan gains +20% phys as fire on kill + other buffs. Also, my gear is far from perfect and i will never have it be perfect because ancestral warchief is a ridiculously slow clearing build and a waste of time to play.
Have no guides, sorry. Everything I mentioned was just off the top of my head. I never really seen anyone make a build using attacks and spells that both deal damage.
Some builds use attacks to proc spells like "Cast on Critical Strike" or Cast While Channeling" both require a attack to cast a spell. But these builds deal almost no damage with the attacks.
Some items to look at that could be useful for attack+spell hybrid are:
Crown of Eyes - Increased spell damage % will also be added to attacks
http://pathofexile.gamepedia.com/Crown_of_Eyes
Kitava's Thirst - 30% chance to Cast Socketed Spells when
you Spend at least 100 Mana to Use a Skill
http://pathofexile.gamepedia.com/Kitava%27s_Thirst
Mjölner - Cast a Socketed Lightning Spell on Attack
http://pathofexile.gamepedia.com/Mj%C3%B6lner
Cospri's Malice - Cast a Socketed Cold Spell on Melee Critical Strike
http://pathofexile.gamepedia.com/Cospri%27s_Malice
and The Taming Ring combined with Emberwake Ring.
Taming = +10% increased Damage per Freeze, Shock and Ignite on Enemy
Emberwake = You can inflict up to 300 Ignites on an Enemy
Both together will give your attacks and spells +3000% damage if you can find a way to quickly get 300 stacks of ignites on enemies.
http://pathofexile.gamepedia.com/Emberwake
http://pathofexile.gamepedia.com/The_Taming