Look at the primary key foreign key relationshsips that have been set up as a starting place.
Since a database without existing diagrams, may not have relationships set up formally, I look at the table structures and names and make my best guesses as to what might be related to what, then dig into the structures to see if there are obvious (but undefined) foreign keys. I look at the stored procs to get an idea as to how the tables are joined and what fields are being queried on.
While automated tools to figure out the database can be spiffy, I find that when I really dig into the details of the database myself, I end up with a much better understanding than I can get from any picture created automatically.