The capacity number mAh (milli amp hours) is a measure of the energy stored in a cell. A 3200mAh lipo will have the same amount of energy in it as a 3200 NiMH but as Ash said, it will deliver it differently. A lipo of the same capacity will be smaller and lighter (excluding any hard casing).
Also, I believe the internal resistance of a Lipo is less so less of the energy will be lost to heat in the cell itself, but don't quote me on that.
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