I would have replied sooner but I was busy doing trivial things ;-)
In the past I've been able to remove the center caps with a suction cup - one of the larger variety that extend to the caps edges. A little light grease on the suction cup might help create a stronger seal so it has a better chance to pull a snug-fitting center cap off. And yes, it's easier to tap them out from behind when the wheel is off the car but if you're only looking to swap them out with something dressier I say try the easy way first.
I got mine at "WallyWorld"!