For sure you will need to tell Hibernate which dialect to use when interacting with your database. And you are correct that you do this inside of the hibernate.cfg.xml file. Since you probably can't use one of the provided dialects, you need to extend Dialect.java to create your own.
Aside from analyzing Dialect.java and looking at the other dialects in the same folder, there aren't any other reference documents.
You probably won't need to do anything with Configuration.java, but it couldn't hurt to take a look inside it. In example, the database I am trying to use is SQLBase. It is not supported by hibernate by default, but there is a JDBC driver for it. After creating my dialect, there were still things that hibernate could not do correctly with SQLBase. In example, SQLBase requires that you explicitly create an index on primary keys after creating a table. To acheive this, I had to patch Configuration.java and rebuild hibernate source.
I saw somewhere that you can get Hibernate to work with Excel, you might want to try to find out how they do that(see what the dialect looks like). Here is a link to HXTT, the folks who have created a dialect to work with Hibernate.
http://www.hxtt.com/hibernate.html
good luck!
mark