I used the duplicolor engine enamel. High heat up to 500: if your brakes get hotter than that your fluid is boiling. Here's the link.
Amazon.com: Dupli-Color DE1642 Ceramic Daytona Yellow Engine Paint - 12 oz.: Automotive
I don't know about painting your sport calipers, it might look tacky considering they are already so sexy. If you have base brakes like me, you should paint them asap since they're ugly as skunk...