Quite a few years ago, the owner of a now long-gone hobbyshop asked me to letter a number of unpainted freight cars…“no need to paint 'em.”
After applying the decals, I wished that I had painted the cars, and if I had had another set of the decals, that’s what I would have done.
I’ve been in this hobby since the mid-'50s, and have learned quite a few things, some by trial and error, others from professionals willing to share their knowledge, and sometimes simply following my instincts.
While you may find the following overly long and tedious, feel free to cherry-pick what you think to be appropriate, and skip the rest.
I have found the complete procedure to yield very good results.
First, I would suggest that you wash the car (or locomotive, structure, etc.), using warm water and dish detergent, then rinse it thoroughly with water and let it air-dry.
Once it’s dry, airbrush it in an appropriate colour(s), then set it aside to let the paint dry/cure/harden, depending on the type of paint you use.
Once that is done, airbrush the entire areas which will be decalled with Glosscote (or your preferred clear gloss) then let it fully dry until there’s no odour of solvent present on the car. Don’t apply the gloss only where the decals will be applied - for rolling stock and locomotives, those areas are usually the sides and ends - cover them completely with the gloss, even if the amount of decal work will be very minimal. Allow the clear coat to fully cure/harden - there should be no noticeable odour to it, (this minimises the chance of the setting solutions reacting with the clear coat).
Next, use a sharp blade to cut the needed decals from the sheet, keeping as far away from the lettering as possible. Once you have all of the required lettering free of the main sheet, use a sharp blade (re-sharpen or replace as necessary) and working on a hard surface (I use a sheet of glass on