The Nose Knows. It should become apparent that I really like having my supplementary light source "on a stick". This gives me some flexibility on the placement of the light in relationship to my subject. You can position the flash to the left or right, or above or below your subject, whatever the situation may call for. But whether your light source is artificial or natural, you can establish a good foundation for effective lighting by aligning the light with your subject's nose.
This lead shot was taken early in the morning during Carnaval in 2008. From the shadows on the street, you can see that the light was coming from camera right, almost perpendicular to the line of sight. Had she been facing me, half the face would have been in shadow and half would be fully illuminated. But by waiting for her to turn into the sun, I got full illumination on the front of her face, accentuating her strong facial features.

A lucky accident occurred when the sun did double duty for this shot. First, it served as a strong accent light that separated the line of his back from the walls of the building in the background. However, light bouncing off a light colored building across the street gently lit the front of his face, separating it from the background and giving the front of the face a three-dimensional effect. The light is so subtle that you might not believe it was really there until you examine the folds of the front of his red shirt. You'll see that the edge is just a bit brighter from the left side, exactly where our trumpeter is facing.

This final image demonstrates that the "nose knows" even at high noon. You can see from the short shadow on the street that the sun is very high in the sky, and while the puppeteer is facing away from the light, his charge is looking directly into the sun. Again, his nose is pointing directly into the main light source. The strong shadows beneath the chin and nose clearly define the face.
So remember that whenever possible, have your main light illuminate our subject's face straight on. As I said, the Nose Knows!
I was at the San Francisco Museum of Modern Art getting ready to photograph an exhibit of prints by the late Henri Cartier-Bresson. As soon as I entered the exhibit, I made a custom white-balance reading which was, for all intents and purposes, the same as the camera's Incandescent pre-set. After scouting the exhibit for possible photo opportunities, I was directed to Martine Franck, widow of the late Cartier-Bresson, who was discussing the photographs from the exhibit and her experiences as a photographer for Magnum Photos. I decided that I wanted a photo of Franck with one of Cartier-Bresson's better known photos in the background. Because the main lights in the museum were coming from tracks in the ceiling I knew there would definitely be shadows in her eye sockets. I decided I needed a tiny bit of fill light to add some life to her eyes. I thought the SB-800 speedlight in my bag would be overkill, so I decided to use the camera's built-in flash. I knew that the light from the flash would give the shadows a bluish tint, so I taped a small piece of Rosco's Full CTO gel in front of the flashtube. This brought the color temperature down to level more compatible with the current (incandescent) white balance.
I set the flash to fire in the manual mode, at 1/32 power. Since I was shooting at ISO 6400, I did not trust TTL when flying this close to the edge of the envelope. This was just a guess, since I knew that if it was too powerful for the given shooting distance, I could partially cover the flash tube with my finger to reduce the output. As it turned out, the setting was just about right.
In a later post I'll talk about light and lighting, but there thing you should keep in mind: Fill light should never over-power the main light. You use the main light to accentuate form and texture in a photograph. You use fill light to provide detail in the shadows. Don't push your fill light too hard or you'll blow out (over-expose) your highlights.
As you can see from the illustration, it's a small piece held in place with some Gaffer Tape. Gaffer tape is tough and can be attached and removed without too much difficulty. I just position it to fully cover the flash tube.
One last suggestion. Be sure to remove your lens hood when using the pop-up flash. This goes against my belief that the hood should be left on at all times, but when a lens is used at wide settings and short distances, the hood can cast a shadow on the lower edge of your photo, something you'll probably want to avoid.
If you're interested in learning more about color correction gels, I suggest you go to the the best source on the planet: Strobist.com. Click here for David Hobby's explanation on how and when to use gels. You can buy an inexpensive sample pack here.
I always have this gel taped to the back of my press pass, just in case.