Gdog - the high temp paint will work as far as not cracking or peeling, but it will severely hinder the cooling effects of the heat sink. the reason it cools, is that the air cooling the aluminium, in turn transfers to the rest of the block, because aluminium has such great heat dissipating properties. by painting the cooling head, u now have eliminated that effect.
however - u also mention that u might want to just paint the top fin. i dont see any problem with that at alll.
hope i helped.