An old trick way back was to bead blast the top of the pistons and then coat them in VHT, usually white color. Then you baked them for a bit. The idea was to provide a thermal coating on the cheap for the piston, keep more heat in the chamber and make a few extra horses. Modified, Comp Eliminator and even some Pro Stock guys did this stuff. I can't attest to how long it held up but to answer the question I believe it would do the heat blocking you are looking for.
In theory, a light-color piece will not let heat through (will reflect the heat), whereas a dark-color piece will let heat through.
That is why "old style" copper radiator are painted black, they let the heat (from the coolant) out better. Lighter colour (shiny stainless steel, for instance) headers do help in keeping the engine compartment a bit cooler.
What amazes me (and is way beyond my comprehension!) is that the color does not have to be on the same side a s the heat to affect its transmission, ie on a rad, the black color is not on the side of the heat, but it does help the heat transfer.
That theory works with any kind of paint, the "VHT" only means the paint will withstand the heat without burning/peeling off. So, if you are painting the roof of your car to keep the inside cooler (yes, it really works!), you do not VHT temp.
So, the simple answer to your question is: yes, it does block some heat. Probably less than real ceramic coating, but might still help.
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