Trial and error.
About how it might have started: Perhaps two people, far in prehistoric times and possibly not even Homo Sapiens, fell ill at the same time. One of them liked to chew on a certain plant while the other didn’t. The chewer became healthy much quicker and some other smart person wanted to know why. They looked at what was different and saw that one chewed on a certain plant.
The next time people got ill with that illness, they tried if they got better faster if they chewed on the plant. They did and so MIGHT have the first ever medical treatment happened.
Edit: From there it was likely “hmmm. This plant works for this coughing illness, but it didn’t help that guy with that sneezing illness. Does another plant work?”
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