The best technique I found is to put your self in the users shoes. What would you like to see from the GUI and put that in front. This also gives you the ability to prioritize as those things should be done first then work from there.
To do this I try to find "layers of usefulness" and add / subtract from the layers until it seems clean. Basically to find the layers I make a list of all the functions the GUI needs to have, all the functions it should have, and all the functions it would be neat to have. Then I group those so that every thing has logical ordering and the groupings become the "layers". From the layers I then add the most important functionality (or what would be used for Day to Day operation) and that becomes the most prominent part, and I work things into the feature around those items.
One of the toughest things is navigation as you have so much to give the use how do you make it helpful and this is where the layers really help. It makes it easy to see how to layout menus, how other pieces interact, what pieces can be hidden, etc.
I have found the easiest way to do this is to start by see what and how your users function on a day to day basis this which will make it easier to get in their shoes (even better is to do their job for a few days). Then make some demonstrations and put them in front of users even if they are Paper Prototypes (there is a book on this process called Paper Prototyping by Carolyn Snyder). Then begin building it and put it in front of users as it is built often.
I will also recommended the book Designing Interfaces by Jenifer Tidwell published by O'Reilly