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The topcoat is just one factor in the painting process. Surface prep is critical. Electrochemical strip is the best but can be spendy. Sandblasting is a good alternate.
Treating the surface with an acid etch (MetalPrep or similar), then applying a conversion coating (GalvaPrep or similar) just before applying coatings ensure the best possible adhesion properties.
As with most cast iron parts, its very porous with a rough surface. The best paint in the world may not stick / stay on that type of bare metal.
There are products in spray cans called Etching Primer. This is a one-coat app that seals pores but also leaves a semi rough (etching) surface.
That etching is what makes paint adhere to the surface. That primer can be had at your local car parts place.
Check out Eastwood Paints web site. I believe they have caliper paint in several colors that can handle the heat.
Their motto is: Do the Job Right.
I used G2 on previous calipers with good results, sorry no pics.
For my C4, I used the VHT caliper paint and baked them on my grill to harden. Also decent results, but I unfortunately baked a little too long/too hot and they yellowed a bit from the Silver they should have been.
I used G2, and the calipers came out great. Unfortunately, glycol brake fluid is one of the best paint strippers, and G2 is not immune where I spilled a bit while bleeding. You wouldn't notice unless you were under the car, though.
Someone, perhaps @PainfullySlow, posted his method for DIY powder coating. That's "the best" option, short of buying pre-coated calipers.
2025 c3 ('68-'73) of the Year Finalist - Unmodified
2025 C4 of the Year Finalist - Unmodified
2025 C8 Stingray of the Year Finalist - Unmodified
Not sure about superior but I used VHT on my C5 a while back. Left them mounted, cleaned with brake cleaner spray, masked them and gave them 2 coats. Car driven daily for 5 years and 60K miles after that and the calipers still looked great when I sold the vehicle.
I've only ever used regular touch up paint and it lasts about 5 years of daily use... the calipers themselves do not get super hot because they are insulated from the rotor by the pads.