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[ZenithTheTV]

If you dont' fully remove the caliper while painting, you have to take extra care that overspray doesn't hit your pads or your rotors. Even if its just a little bit that you can't see could compromise your braking ability later on.

As for the calipers being cadmium plated, it means that any paint that will stick to them will require quite a significant amount of spraying, so I really don't see how you're going to be able to do it with the calipers still mounted.