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So I want to bulk build some Pskyers (hate the I've got a headache official ones) and I'm planning on using Cadian torsos and legs but they really need heads and arms that scream Pskyer. Any suggestions that look Imperial and not to scruffy like the flagellants?

Seems like you're going for a more regulated looking psyker. Less 'disheveled crazy person', more 'cold iron will of the Emperor'. Personally I'd say use Inquisition Crusader models, chopping off their shields and replacing with pistols.

Otherwise try using some of the space marine scout heads like the visored helmet, and use regular cadian arms with staves in their hands.

My Inquisitorial Warband psykers are made from Imperial Bowmen (fantasy) and Chaos Cultists (40k).