Is there anything to stop the core devs saying we want unlimited bitcoin and changing the code to allow it. I mean, 21 million isn't much.

You're already a senior, but looking at what you are stating here, I guess you really don't understand how crypto works right?
More simply how the world trade and economy is going well. If the supply is made unlimited, then there will be times where it will only become rubbish, as well as things/toys which just trending in one season.