I have filled many an overflow bottle from just low coolant and over-heating. Steam alone can produce a lot of pressure, that got trains to CA. I would certainly do the gas test first. I still have a kit from CA Customs or such w/ test fluid that is supposed to turn yellow if you suck combustion gases from the radiator top. It never indicated anything on any car I tested. Usually a head gasket leak will put messy oil into the coolant, and I mean a thick brown mousse like the La Brea tar pits, not just a thin oil film.