So, the other day, I found this great website that helps loads with designing colour schemes and picking out spot colours. http://colorschemedesigner.com/ It has loads of useful features, and you can view the way different types of schemes work together.
You can view how many styles of applying colours work by clicking on the small dial type circles above the colour wheel. Within the wheel itself there will be one or more dots (dependent upon which dial you've selected) which you can drag around the wheel in either direction, and this will show suggested colours in the big square on the right. Not only this but you can adjust the palette too, which I've found invaluable.
Worth a look.