Two details most people skip. The first is that copper could be founded in natural deposit on the surface, so we see a lot of copper tools and weapons way before ore extraction was a thing. Also people could noticed that heating it made it nimble for working it and cleaned that green stuff (oxide). At that point someone could had figured that those green stones laying around near were we found natural copper are the same green that oxidized copper, so was worth a try heating them up.
The other is different places experienced different evolution, the most extreme example is some African cultures skipping cooper and bronze and jumping straight to iron, wich probably had something to do with pottery or meteorite iron
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