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I currently have 2 armies Tau (4,500 pts) and Dark Eldar (2,000 pts) and Im considering starting a new army.

My one option is to make a Renegade Space Marine chapter that is undivided though there are 2 groups one that worships Slaanesh and the other that worships Nurgle. So while most of the army is out for themselves these two groups have chosen to devote themselves to those to Dark Gods. Though with this army I can also use a Space Marine list since I wont paint the cultists in the colors of either the Plague Bearers or Noise Marines. The fluff that I have for them is that the Chapter is going through a Civil War. Part of it wants to break free the other is choosing to remain Loyal. So both sides will still be painted the same just with a few minor differences.

Though Im also considering a Witch Hunters army. I want to keep it pure in the sense that Im not including allied forces. Though I have not played many 5th edition games so are the Witch Hunters/Sisters of Battle any good in 5th? Way back when I first started playing Warhammer the first time was Witch Hunters around when they first came out and I would love to play again. The fluff I have for them is that they are a chamber militant under the service to Inquistor Constantine.

I loves my Witch Hunter/SoB army. I find them hard to play to their full potential but that's because it's my first in like 10 years.
If you've played your two current armies a lot, I'm pretty sure you'll find them decent enough.
Only thing that sucks now are the CC models. Death Cult Assassins seem to suck a bit due to piling in, for exemple.

Codex: Witch Hunters still does well in fifth; I tend to beat everyone other than Orks. The main issue is that your unit selection is fairly limited if you want to be competitive. Some units were awful even in third edition (eg Sisters Repentia), but others have aged badly (eg Death Cultists). It largely depends on what you want to run: a Mech-Sisters force is highly competitive, whereas an Ecclesiarchal hoard (fooslogging Sisters, Frateris Militia, Penitent Engines, etc) is purely for fun.