Depending on the situation, they basically mean the same thing, except that you would not use them the same way.
For example, you could say either, "I have two reasons," or "My reasons are twofold." You cannot swap them. Twofold also means doubled, although I'm not sure that makes it any clearer.
There is a similar word. "manifold," which is similar to "twofold" except that it means "many." For example, you could say, "I have many reasons," or "My reasons are manifold."
You would not use twofold or manifold with physical objects. For example, you would not say, "My shoes are twofold," or "The flowers in my garden are manifold."
These words are fairly formal and not generally used in casual conversation.