I keep Skype turned on all the time. It's set so I have to manually turn on video. I'm not always presentable for video calls.

Here are some tips for having a better video presence.
Increase the lighting. I put a light set up on the desk behind my netbook to make me a star. It's better to have a full spectrum light for the most natural look. You might want to try different lamps in the store to see which light is most flattering to your facial skin tone. Adjust the height of the lamp to allow some features to appear natural and not flat.
Improve the background. I once had a caller ask about what was hanging behind me. It was some laundry I was drying.

I changed my setup two ways. My SOHO desktop Skype computer is against the wall so I put up a curtain behind me to block the view into the room. When I travel, my netbook Skype computer is usually on a desk so I turn the desk to point the camera toward the wall for my background. Of course I choose an attractive wall.
Another way to help is raise the computer camera to eye level with books or a travel bag so you don't hunch over and the camera is not shooting up your nose.
Sound quality is ruined by your voice bouncing off walls in a large room so put something behind the computer to trap your voice more directly into the microphone. Move a cabinet or hang a suit behind the computer.
Speaking of clothes, it's a good idea to have a pullover or a jacket handy to hide the fact that you just stepped out of the shower...unless that's the look you want!
Enjoy your video connection for business or with family.