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Generally the immune system doesn't work that way. The immune system generally targets living organisms actively attacking the body. Immunity derives from learning how to efficiently kill the organisms, often after a single encounter, and "remembering" that for as long as possible.
The defense against toxins is a little different. I don't have as much knowledge on that side, but generally the defense against these kinds of things is achieved when a cell is damaged, but not killed by the agent heals in such a way that it's less susceptible to that agent. Kind of like a callus forming on a part of the skin that gets repeatedly damaged. Also, the systems of the body that are responsible for clearing out toxins become somewhat more effective at getting rid of them after repeated exposure.
So, vaccination generally relies on training the more active defense by specialized cells that are specifically "designed" to be trained and "remember" how to attack the organism, but not as much a reaction by the cells that are being attacked by the microorganism. Whereas toxin defense is more a reaction by the affected cells themselves as well as increased efficiency of the body to filter it out, but the affected cells don't really "learn" how to protect themselves in quite the same way.
But this is all generalization. There are many types of venoms and some can be affected by the immune system, but in general it's a very different type of response that requires repeated exposure and recovery to develop.