I remember back in the dark days (1998) trying to work with vector (I started out with Corel Draw 5). It was the most frustrating thing I ever tried! I couldn't do anything other than draw simple shapes. With that in mind, I still approach vector drawing in much the same way, breaking down the image into simple shapes then adding to or expanding on those shapes. Sprinkle in a litte color and a gradient or two and there you go.
The images in this gallery are all 100% vector (Adobe Illustrator).