The best paint to use is true caliper paint. Some people swear by engine paint because it is suppose to resist heat and high temperatures but does not fare very well down in the braking area. From my personal experience and research, the best paint to use hands down for something like this is true ceramic based caliper paint. Painting calipers and brackets is a very easy task, and the only thing that you need to remember is to take time to prep and CLEAN any surface from any existing dirt or grease before applying the paint.
Here is a link to what I and many others have used. I think I got my kits off
ebay for about $25/ea IIRC.
G2 - producer and distributor of the G2 BRAKE Caliper Paint System Set and other high quality carstyling and performance products.