I agree with whoever said it looks like a modern car type pressure cap and if you inspect it you may well find the pressure. More likely something like 250KP than PSI. However, that does not mean it is a pressure cap, it may not have the pressurisation parts inside it, it could just be an automotive expansion tank plus a modified automotive pressure cap that can't hold pressure.
The easiest way to check is to put it in your mouth and seal around the rubber ring with your lips. Then give t a good blow. If air passes through it is not a pressure cap, if not, then it is.
If it is, I would suggest it will be set to vent at something like 15 PSI.
Using it as a pressure cap MIGHT reduce the evaporation rate when hot but would make leaks a bit more likely, but I would be happy with it. I don't think this is what is meant by a pressurised system in central heating terms, that uses an "accumulator" to hold the top-up water and allow for expansion, just like a domestic combi-boiler. That presents a problem with repressurising with a ready mixed antifreeze mixture. Whereas all you have to do is remove the cap and pour a bit more in.
If you really do not want any pressure in your system then a small drill up the hole in the centre, bottom of the cap to destroy the valve would do the job.