Common problem with alloys, they "rust" to the hub.
Put the bolts back in loosely then, with the car jacked up and , preferably, on a stand, give the tyre few kicks.
If the wheel still doesn't come off, tighten all the nuts up then slacken them one or two turns.
Drive the car back and forward a few yards and brake very hard. This will usually crack the seal, but I've seen us have to drive it on and off the pavement a few times if they're really stubborn.
Before refitting wheel, give the area that contacts the hub a very thin smear of copper grease so it comes off easier next time.
Best to do all the wheels now, rather than finding one stuck when you've got a puncture on a dark wet night in the middle of no-where!
digger, August 2009