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Since Milani is the CG deity of hope, devotion and uprisings, she is a perfect fit for PCs in this AP: she is the goddess of freedom fighters after all. As such her priests would be quite far removed from priests of Abadar, or even other major Korvosan deities like Pharasma or Asmodeus. Sarenrae or Shelyn, the other two gods who have their own temple in Korvosa, are closer to Milani in spirit, although they do not encompass the thought of freedom fighters. So I'd be inclined to have my player stay with Milani.
Any faith could have warpriests, I guess, they'd just be the church's faith militant branch. Of course, gods who actively fight for their causes, would be a better fit for the idea of a warpriest, so Sarenrae who stands for peace or Abadar who promotes law and civilization would probably be less inclined to have such warrior-priests in their ranks. Again Milani seems like a better patron diety for warpriests than any of the gods in Korvosa.
Hellknights are lawful and allow any lawful alignment in their ranks: LG, LN or LE. The order of the Nail holds members of all these alignments, although LN and LE are definitely represented more than LG. As far as divine Hellknights go, any lawful god will do. The Hellknights will just play up the lawful aspect and tune down the good or evil side of their alignment. Having a Hellknight PC is a possibilty, as several GMs have allowed it, but it is difficult to juggle. The PCs will 'fight the power' in this AP, which tends to conflict rather heavily with Hellknight rules.