Quite a few users find some of the terminology and accounting processes a little confusing at first. Some of the more popular small business accounting packages tend to hide these aspects of book-keeping from users for simplicity, so with the current user interface there is often some new ideas to grasp.
First step is the manual - the LedgerSMB manual is free and highly recommended reading.
If you would like some background on general accounting practices, there is an (unassociated) tutorial So, you want to learn Bookkeeping" which seems a good place to start.
Another excellent resource is second-hand book stores. Lots of MBA studends sell off their textbooks (presumably to finance their first business rather than pay of gambling debts) so second-hand bookstores will often have very good texts on accounting at bargain prices - these can make great reference books.
Finally it would be remiss not to recommend securing the services of an accountant to help you out with the finer points from time to time, should you feel the need or have a legal obligation to do so.