Many people have done this quite successfully. However, you need a high-temperature paint, or you risk setting fire to your brake calipers. Folia Tec (888-486-0067) sells speciality caliper paint in a variety of colors. Other people have used engine enamel, exhaust manifold paint, Tremclad rust paint and bar-b-que paints. Some paints are air-dry, while others require baking at high temperature to cure. It is essential that the brakes be clean and masked properly before painting.
No matter what paint you get, track-driven cars can count on getting brake dust embedded in the paint, which will deteriorate the color. Street-driven cars need not worry, since the brakes rarely get hot enough to cause the brake dust to stick to the painted surface.
Check out YouTube - How to Properly Paint Your Brake Calipers
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