A few of mine. Mind, you can add your own suggestions to mine as I can to yours. :)
Lucas - Pequeña Serenata Diurna (The song's very first line is "I live in a free country"...) , The Pirate King (Yeah...)
Cass - Hare Hare Yukai (Not that the rhythm fits her, but, with Cass, you can't go wrong with an anime soundtrack about a character that imposes anime tropes!) , Calico Skies (Calm, soft, nice...)
Selene/Neruite - Spaceballs, The Ballad (It actually will be a plot point soonish! There's a reason!) , I'm Only Sleeping (And so is Endymion...)
Pastor Edward Duke (from the first Robert debacle) - Jesus He Knows Me (Heck, it was the title on one of his episodes)
Matt "Sider" (the mad scientist) - She Blinded Me With Science (Yeah, it's the version with the best sound I could find...)
Robert - Ebony and Ivory (Self-explanatory)
Maxwell - Mother Nature's Son (Also self-explanatory...)
Others to come as I think of them. ;)