Someone explained it recently in another thread/forum- its basically to do with the charge process not being 100% efficient, so the charger may often push more current to the lipo than actually goes in as such. Also, the lipo's mah rating may not be 100% accurate due to god knows how many factors to do with construction and chemical composition over time etc etc.
Discharge rates is only important when using (discharging rapidly) a lipo- the higher the C rating, the quicker it can be discharged & therefore the more punch it has, although capacity is also an important factor combined with C rating, in order to calculate the total amount of current it can push.
4s 5000mah x 20c = 100amps continuous, 1440 watts.
4s 5000mah x 25c = 125amps, 1850watts.
4s 4900mah x 25c = 122.5amps, 1813 watts.
5s 5000mah x 20c = 100amps, 1800watts.
They are all fairly even in terms of power potential and current output, though the 1st one may be a bit warmer by the end of the run. If you gear for the same speed with the 20 & 25c 4s lipos, I doubt you would notice much of a difference really- maybe if you turned down the punch the 25c lipo would turn out to be a little more 'feisty' under acceleration, but I wouldnt worry about anything really.
Posted my lipo yet?