It would be worth working out who you want to mainly perform for: The radio hosts, or the home listeners. Also whether you will have people call in etc.
Banachek has a CD set out there called Radio Magic that is full of advice on this sort of stuff. I cant review it or fully recommend it as i dont have it...but I trust Banachek's work.
Will you have a chance to do some pre-show beforehand? You can create some truly impossible psychic demonstrations for the home listeners if you do a little pre-show between songs or before you go on (You could use psypher here).
Don't worry about finding the perfect 'trick' - the real secret to mentalism is in the presentation. Even the most basic mentalism effect can be dressed up to look (and sound) impossible.
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and wondered if the Magic Café crowd could point me in the right direction.
Better go ask them, then.
Rev.