I don't think so. The heat you are describing is a result of the CAT in the mufflers. That's how they work. They get red hot inside in order to burn any unburnt gases that did not get burnt in the combustion chamber. By virtue of the fact that it's a 3 dimensional sieve, it is a restriction to the flow of the gases. To contain that extra heat, the internal canister that encapsulates the CAT is twice as thick. They are way heavier than TOR's.
The extra heat that the CAT creates then migrates forward to the crossover you are referring too and this is why you are feeling it in that location. As soon as you move from a stop, the external flow of air (and internal flow of gas to some degree) cause the heat to migrate rearward towards the CAT
again.
I don't think ceramic coating will make a noticeable difference for you and it's money you could save towards the header pipe. If you can afford the TOR's do that first, and if you can't and/or prefer lower end torque and quieter (closer to stock) sound do the de-cat. Either one will be cooler than ceramic coating the pipes in my opinion.