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yes, herbalists and healers would have access to and knowledge of fast-acting poisons.
there are plenty of plants like nightshade that can rapidly kill a human, and those familiar with plant life would be well aware of that.
hemlock isn't as fast acting, maybe a few hours before death if you ate it, but that's how Socrates was executed 2400 years ago, and according to sources it took about half an hour for him to die, so knowledge of fast-acting poisons is very old.
https://en.wikipedia.org/wiki/Taxine_alkaloids
An extremely common tree that people grow as hedges and cut into fun shapes.
In animals the only sign is often sudden death.
As you correctly surmised, most poisons wouldn't act nearly as fast, although there are exceptions. In reality, people would just get very sick for a very long time and perhaps not recover. It would've been difficult to even correctly identify poison over illness or food-borne pathogens. I'm willing to bet a lot of people who died of natural causes had their deaths attributed to poison because of their position and lack of medical knowledge as well.
Then again, some poisons and their effects were well-known to contemporary physicians or their forebears, so depending on the precise effects they could possibly deduce what happened in some cases.
the slow moving poison was a weapon, meaning it was slow and easy to hide from.
quick acting poisons have been known but even in the era before enlightened thought, lots of knowledge was aware of them. they just did understand the why
we know now, most of those quick poisons would be so far out of the bodies pH that it would shock your system instantly
today we'd be able to revive someone that might have taken something like that but back then, if it doesn't look like your breathing and they couldn't hear your heart... you dead