I recently gained a little more understanding of fuel MISmanagement when I visited a friend that just bought a Cessna 310. Now granted, all of my experience is in a SE Cessna with gravity fed (high) wing tanks or with my Bonanza that has two 40 gallon wing tanks.
His 310 hast two built in tip tanks, which are the MAIN tanks. It also has 2 (or was it four) auxiliary wing tanks.
The fuel systems returns unused fuel to the mains, so if you start off on the aux wing tanks, the return lines will hit the full mains and be dumped overboard.
After you run some fuel out of the main tips, you can switch to the aux tanks, but if you didn't burn enough out of the mains, they will be refilled by the return fuel and could possible dump more fuel once the mains are again full.
That to me seems really difficult to keep up with, especially in single pilot IFR operations. I guess you get used to it though.