In order to really understand behaviour, I like questions of the form:
"I'm interested in a time when you had
to solve a very difficult problem in
R; what was the problem, how did you
approach it, what obstacles did you
have to overcome, and what was the
result?".
Look then for all the things you want in a team-member - a good balance between "I" and "we"; a clear, logical thought process; a willingness to admit to and overcome difficulty; clear communication with their customer; etc.
Beyond that, the usual skill/quiz type questions are useful if you want to test deep knowledge of the skill-set. Pick a couple of sample problems and ask them how they'd go about solving it, looking for the breadth/depth you're after.