PRR steam painting instructions as published in the PRRT&HS magazine were pretty complete and a little complicated. They state that the frames and undercarriage, I think the pilots, and the truck frames on the tender were to be painted black. The boiler, cylinder covers, cab, tender tank were to be DGLE, Dark Green Locomotive Enamel). Basically everything above the frames was to be Dark Green and the frames and down black. IF you look at the dark green next to black, you can see the difference. When it stands alone, it is very near to black to the eye.
The Cab Roof was to be a mix of brown and freight car color (boxcar red). I forget the mix but it was a little darker than freight car, so a reddish brown might work.
If you really want to get fancy, they window frames on the cab were to painted bright red.
I have a friend who has been very successful using Krylon spray bombs. I have used them some on buildings and it worked fine.
ScaleCoat Paint now sold in hobby shops and made by Minuteman had the PRR colors in bottles. I don't know if they also do spray cans.
A nice touch is to also decal the loco number on the sides of the headlight and backup light.