I have been asked many times how I manage colors in Photoshop and mainly how I pick them using the tools available in this software. To be honest I have never been a huge fan of Photoshop Color Picker.
First of all because I find really annoying to open this window (even though there is a F6 shortcut) that interrupts the workflow. Second because I am maybe really used to work with the Corel Painter Color Picker that I consider optimal.
This is the default Color Picker in Photoshop:
In Photoshop CS6 you have now the opportunity to pop up a Color Picker HUD but I still consider this one a little bit tricky and not handy because you have to press Ctrl+Alt+Cmd keys. Even though you could on your Wacom Palette assign those keys to any button I still believe this is not the best method for picking up your colors.
Fortunately Photoshop allows us to choose not only one method: Standard Color Picker, RGB/HSB/CMYK Sliders, Swatches or even third party extensions that can do the job.
Let's talk about these last ones and especially three of them: Kuler, Painter Wheel and Coolorus.
The first one, Kuler, is already by default in your Photoshop extensions. You have to select Window>Extensions>Kuler. This will open a basic color wheel with a luminance slider. The advantage of this color picker is that it can be always available while working and last but not least a really nice feature that helps you building complementary, monochromatic, compound, shades and triad schemes.
The second one, Painter Wheel, was one of my first extension I used. It simply reproduces the Corel Painter color wheel. A circle color wheel with a triangle allows playing with luminosity and saturation. Just great!
The third and last extension is named Coolorus, which is a combination of the two previous ones. So you will have a Corel Painter color wheel with the ability to construct your complementary, triadic, tetradic, etc... schemes. I encourage you to give a try to this one and support his creator.
This is obviously not exhaustive because you can find other third party extensions but I have tried to sum up what I consider the most relevant and useful. Hope this can help you. Enjoy!