I teach Lightroom and Photoshop on my workshops. Sure, we always try to get it right in camera, but there are times when the light is just not right for a good image.
Take this silhouette for example. The available light was flat and cold. By adjusting the Levels, and then by increasing the Contrast and Saturation, I was able to turn a flat shot into a fab shot.
Always try to envision the end result. It's kinda amazing what you can do in the digital darkroom - as long as there is detail with which to play. Here, if the sky had been too overexposed, there would not have been enough workable detail. Tip: always expose for the highlights - the brightest part of a scene.
For more tips on lighting, check out my apps.
Explore the light,
Rick