Painting Brake Calipers and Drums?

Just the caliper paint, and clean calipers and drums (or new drums, if they're close to needing changing anyway) for the best results, a primer won't work. I'd recommend paint rather than a spray can as it's far easier to get it exactly where you want it, and only where you want it. Paint them whatever colours you like, I don't see why what you're planning would look strange!