I've often found that one of the funnest ways to create a color scheme is to use photographs, as they already naturally full of interesting relationships between colors reacting to light.
- Press on the 'New Pic' button on the top right of the screen to upload your reference photo
- Viola! Consider the colors it has automatically picked from the image
- Click on any of the color tiles to copy that hexkey to your clipboard for future use
- Keep this window open as a reference when plugging in your colors to your color scheme, whether it's in CSS, photoshop, MS Word, or something else.
Suggestion: You obviously don't need to use every color that's been pulled from the image. That'll get messy. Pick the ones you think go well together. Suggestion two: Photos with a unified light source often work the best. That's because the colors will have some sort of relationship with one another.