If you have trouble remembering the difference between Lightroom's saturation and vibrancy adjustments, Thom Hogan has a nice photo illustrating the difference over at his Nikon Field Guide.
The gist: increasing saturation boosts all your colors by the same amount. In contrast, vibrancy works non-linearly by boosting less-saturated colors more than colors already approaching full saturation. It's a little like the difference between using the tone controls to brighten a photo and using the contrast slider. The first approach gives you more control; the latter can easily overwhelm the photo.
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