It make be very obvious however I just want to be absolutely sure before I proceed.

I have read a few threads where some people use Permatex Copper Coat to assist in head sealing. Do you just spray the whole combustion chamber? Do you mask the sealing surface off or just spray everything? (I could only find a spray version, is there another type?)

Permatex with the indian head on it is what I have used. Whether or not is another argument. The bottle has a brush in it. If you are using head gaskets (please dont) then you would apply it to those as it is gasket dressing rather than sealant. For the barrels to the heads, I am not sure.

I use the aerosol. I just spray a good coating all over the sealing surfaces. Don't worry about getting it on the valves, it won't hurt a thing. I let it set up before installing the heads.

There you go, the expert himself