I'm not sure if I'd count Shirtliffe in with the confederation, at least under the current regime. She's on record as saying her loyalty is to Lilith Grimm, who has given us ample reason to believe that she isn't the confederation's biggest fan, even if it's too risky to oppose it publically.
Also I'd be inclined to agree with TealTerror about Saffron except that it's been shown that she can't help herself: She screws people over even when it isn't in her interest to do so. She tells herself it's all about the money but she's actually just acting out whatever psych issues she has again and again, Early is the same way both of which say Chaotic Evil to me, though with a convincing mask of sanity. I'd say Jeyne is the best Neutral Evil character for firefly, though one who may be headed for redemption.
I'd say that Simon proved his good alignment when he risked blowing the Ariel operation because he couldn't resist saving the guy having a heart attack in front of him. His promising not to hurt Jeyne could be argued as Good or Lawful equally but overall I'm inclined to go for Neutral Good for Simon.
Also : http://i107.photobucket.com/albums/m287/snake0/batman_alignment_chart_fullsize-1.jpg