this is an AWESOME example! what sort of light are you using here? i've been looking into getting a sort of multi-function light to start learning better lighting techniques. i'm one of the guilty who rely mainly on natural light, so i'd love to delve into another realm of lighting.
Shot's like this are pretty simple. When you have a bright sky, and a darker foreground, digital cameras can't handle the dynamic range of light. I think our eye sees 16 stops of light, and our cameras can work with 5 or 6. This is why if you expose for the sky, you get a silhouette of your subject sometimes. If you expose for your subject, you blow out the sky (which is what I did in my first example).
So, set your camera on manual, and your shutter speed to its highest sync speed (around 1/250th for most cameras). Now, adjust your aperture to expose properly for your sky. Better yet, underexpose it a stop or two to make it a bit more dramatic. Pop a couple of frames. You will probably have a great background, and a really dark subject.
Now, we need to deal with our dark subject. Throw a flash on a stand aimed at your subject. Set it to manual power, and start at around 1/4 power or so. Take a shot. How does it look? Subject to dark, turn the flash up to 1/2 power, move it closer to the subject, etc. Subject to light? Turn it down or move it back. Eventually you will have lit your subject to where you like it. You can use a meter to do this quickly, but honestly once you do it a few times you realize how easy it really is.
What you are doing is compressing the range of light. Make your bright sky a little darker. Make your dark subject a little lighter. All of a sudden you've got your whole picture in a range where the camera can expose for it properly.
The cool thing is that you are lighting now on two planes. You can control the exposure of the background and your subject independently. Very powerful, and that's only with one light. It gets even more fun when you modify that light, soften it, harden it, colour it, etc. Add another couple of flashes and you are going nuts!
Go to strobist.com. Read it all. Read it again. Then, read it again.
Hope that helps!