When we paint Calipers at the shop we like to sand and prep VERY well, Then use a epoxy for a sealer then use a good single stage product for best durability. Not only for the heat but also for resistance to brake fluid.
I have also used a base/flat clear on a set and it held up good as well. Not as good to brake fluid but handled the heat fine. I think the most important thing is your prep work and using a good epoxy primer.
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