You start by having fires. Then you start putting circles of rocks around the fire to help with containment. Then you notice that occasionally some little shiny bits melt out from those rocks (copper and tin) and harden on the ground later after the fire is done.
So you start to collect it, and eventually collect enough to start using it for tools. Then you start actively seeking it out. You start by just looking for surface rocks, but then you start to go into caves and find them. Eventually, you might even see it in the cave walls and start trying to break it out of the walls.
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