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Check with your GM first. Those Hellknights will be antagonists in a certain campaign, so making sure your GM has nothing planned is ideal.
I have not played a Hellknight yet, sorry, but if you are thinking about doing something different, I'd try a Cavalier of the Order of the Star x/cleric 1. Order of the star gives you nice charisma synergy and allows one to stack cavalier and cleric when it comes to channeling energy.
That said, your class combo might work as well, though I can't remember the base attack bonus minimum for the PrC, as long as you don't concentrate too much on wisdom. Smite chaos is pretty good for this campaign, since its checklist of creatures nicely fits the matrix of foes you'll face during the campaign so some charisma is ideal and relying on several mental stats might cost you.
Unless you're starting out high level then I'd say no. One of the prereq's for becoming a hellknight is killing a demon with an HD higher than your own in view of another hellknight. I don't see any level 1s single handedly killing a demon, even a quasit.
Also, a hellknight is its own prestige class. You could mimic a hellknights features somewhat with multiclassing other classes but that still doesn't make you one.
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There's a hellknight in the group I run, he started out as a cavalier. He's doing just fine in the campaign, we're currently lvl 14 and in Xin-Shalast.
He has reached the rank of Paralictor and has been given command of the outpost of Ft Rannick, and established it as an Order of the Nail bastion to bring law to the wilderness.
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I have a player who wants to go into the Hellknight Prestige class. He is currently a 12th level Arcane Duelist Bard and would go into Hellknight for his 17th level (he doesn't get heavy armor proficiency until 16th Arcane Duelist).
I plan on extending my RotRL campaign well past the actual series of modules.
I have a Chelish paladin of Iomedae in my RotRL party. The character is also a minor Chelish noble, being the youngest daughter of the Duke of Kintargo. In her backstory, she trained as a Hellknight in the Order of the Nail in Korvosa, but after putting down a peasant revolt, came to realize that order without morality is wrong. She resigned her commission, and took vows as a paladin.
The Hellknight backstory has come up occasionally in-game, and I gave the character a couple of minor bonuses based on the awesome Golarion-specific backstory. (e.g. she has Infernal as a free bonus language, and I let her have a +5 on Knowledge (religion) checks to identify devils.) Aldern Foxglove made some reference to her background in one of the letters he sent to her, as well.
I had planned a side-quest in Magnimar where the local Order of the Nail issues a reactivation order for her, and the paladin is faced with a quandary: to accept the reactivation order or not? I decided not to run it because the player was having some RP issues dealing with a bad choice made earlier, and I didn't want the player to think that I was trying to engineer the paladin's fall. (I'm not-- I really like the character, and paladins in general.)
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One of my players is a Hellknight. He's a CAV/FIG Making sure that the Swallowtail Festival went on with out a hitch. He stayed in the city to combat the savage goblin hordes. He's come into conflict with some of the more chaotic members of the group and some of the local Sandpoint PCs see him as being the "Fed" cominging in from the big city to tell them what to do. Over all it works well. He will take the Hellknight PC, but I'll save the fight with the demon for when the game moves to Magnimar.