Welcome...
There is a wealth of information on the wesite about Hibernate usage. A good starting place is
http://www.hibernate.org/hib_docs/examples/quickstart/html/quickstart.html After that try browsing the documentation and building up some more complex use cases building on the quick-start or examples package.
Personally, I don't use any of the generation tools. And especially for new users, I would think it would be of great value to start off with some very simple use-cases with hand-coded classes, manually-edited mapping files and manually-created database tables. That way you can see how all these pieces fit together and interact. And, perhaps even more importantly, you can directly see issues/errors that Hibernate will complain about and how to resolve them. Then add in the additional complexity that comes with another tool layer. To me its a walk, then run situation...
It might not seem like it now, but the mapping in Hibernate is fairly easy to understand and write after you play with it a little bit.. I also have used TopLink, and can say without a doubt that I could now map entities faster in Hibernate than in TopLink using its UI.
Anyway, HTH