unaligned?
don't you mean 'misaligned'?
think ab9out this for a second, which do you think would put more sideways forces on a wheel and tire, forcng the front end out of alignment...
two cans of spray paint weighing a few ounces, or the force of stunt driving, and smacking things like curbs, parking bumpers, and of course potholes.
another thing to consider is that when you paint a rim you ( normally) paint the entire thing evenly so the entire wheel gets an even coat... so, whatever extra load to paint might cause on the wheel would be evenly spread out as well...
As opposed to the force you put on a wheel and tire from smacking a curb, which would be localized, focused, and very directional on one specific area of the rim...
If it were me, I would have them spin balanced any way simply because I had them off the car, and it was a good time to inspect tires, wheels brakes and suspension while i was in the neighborhood... less than 10 bucks a tire and it helps me get the most out of my gas mileage and my tires... whats not to like?