The problem with Copper Kote is the ratio of copper to the vehicle which is basically just glue. Spray Copper Kote gets more copper on the surface as more of the carrier evaporates especially if you give it multiple coats. I've used it to stick larger heatsinks on Asus GeForce cards, the chip temps dropped quite a bit according to the Smart Doctor monitoring utility so it must have worked. I'd just use Artic silver for CPU's though as masking and spraying is such a hassle to save a buck.
Copper gasket sealers were developed initially for coating diesel engine head gaskets(made mostly of copper), the super high compression ratio on diesels really heats the cylinder heads, some of this heat needs to be transferred to the engine block through the head gasket. Some engine manufactures specify it while others don't, just requiring a meticulously clean mating surfaces so the jury is out on whether copper is necessary in engine applications.
I'd say use it if you just stepped on you're only tube of RS goop, the stores are close and you want to get your new system running.