Rusty Claymore-
As Jaden has said, tutorials are helpful. Familiarity with the program's interface is the first big step. Once you feel confident it just takes practice
Extrusion modeling is a good technique to start with (actually that's all I use right now).
RidleyofZebes-
Blender is awesome!!!
You will beat yourself up over the counterintuitive interface for a good while, but after that it makes perfect sense.
It has a lot of powerful features, unfortunately I'm too lazy to do much past basic stuff. Getting a background reference image set to use for extrusion modeling works pretty well. Then it's on to the texture mapping and animation.