Downloaded LTSpice day before yesterday. Printed up the "Quick Start" guide, and was up and running in just a few minutes. Nice interface and waveform viewer.
I had the luxery of having used Pspice in college, so I was part of the way there to start with. I think there are still some good reference in publication for Pspice, which by the way, forms the foundation of all or most of the circuit simulators. Maybe LTSpice has good online docs too, don't really know about that. But if you've had a hard time getting started, try the Quick Start guide, and then ask questions here. Help is available.