Yes, the brakes can get pretty hot.

For simple brush-on paint, Just remove the wheels, mask and use this type of product:
http://www.duplicolor.com/products/caliper.html

Here is a two part brush-on expoxy paint that may be more durable - but have all four calipers ready before before mixing the paint and the hardner
http://g2usa.com/brake_caliper_paint.shtml

You can't go wrong with red IMO

I used this paint because and it was a better match with the Aero Blue

http://www.duplicolor.com/products/engine.html - DH 1612 High Heat Blue

You can buy the brush-on kits at most auto parts stores for around $30

Hope this helps