People started with pure metals. There is a small amount of pure gold, copper, etc. that is laying around in nugget form. There used to be a lot more of it before humans gathered it up. Iron does not last long in the environment but can be found in pure form in meteorites.
So even before smelting was discovered in an area, the people there had access to pure metals and would be familiar with metals.
They then would find ore with nuggets in them or flecks of pure metal. So they would know that the rock had metal in it.
Smelting itself probably happened by accident at first – by using ore to build fire pits and having the metal melt out. This would be incredibly rare, but keep in mind that humans are 200,000 years old and have been using fire that entire time (pre-humans learned how to control fire) and many places never learned metal smelting on their own.
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