Pretty much trial, error, and happy(or unhappy) accidents. People tried feeding or use specific plants on wounds or sickness. What worked kept being used.
Its also worth noting a lot of old medicinal herbs tended to be either placebo, a sedative that made you less likely to care about your symptoms, made you vomit up whatever was making you sick, or made you shit out whatever was making you sick. herbs with actual medicinal value beyond purging your GE tract were more uncommon.
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