@schemeshot, thanks for asking. It really comes down to education. Buy a really good field guide book or two with lots of pictures. Even better if it's tailored for your specific region. Also search online or join a local mycology group.

As far as psychedelics goes I only know of two types of groups. Those mushroom containing Psilocybin and those containing Muscimol. The first one is typically found in what people often refer to as magic mushrooms. Probably the more potent of the two. I have exactly zero experience in this, it should be said. They are basically illegal almost everywhere, so I don't even go there. The other is what is found in certain varieties of Amanita mushrooms (think super mario bros.) such as the Muscaria. Although legalities are not really an issue here, the problem is that certain varieteis of Amanita are poisionous to various extents. Some are even deadly poisonous. So all I can say here is stay away unless you know what you are doing and understand the risks fully. Good luck!