Thousands of years of experience, basically. Nowadays we can just look them up on the internet.
There’s some pretty scary looking stuff that is totally edible and delicious, like sea urchins. Or consider that we eat oysters, which pretty much look like rocks with snot inside of them, but they’re delicious too. And non human animals eat them too.
Like others mentioned, typically by experience.
One rough rule of thumb is that if it is highly colorful with lots of patterns, chances are it is poisonous. This is something known as aposematism – certain species develop these bright colors and patterns as a defense mechanism to warn predators. (There are many exceptions of course, with some colorful species being delicious while other innocent-looking ones are highly poisonous. Best to avoid eating random things from the ocean if you don’t know what they are.)
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