For a really good example of why you should develop your painting in all areas at the same time and not just throw in a background later, check out illusion #3 of these three optical illusions from echalk.co.uk:
Even if you know it already, it will amaze you to see just how much context influences your color judgement.
...and on a somewhat related note, here's an old (pre-blog) page of mine on how to hone your color judgement using Photoshop and a digital camera.
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