as mentioned, you have to use your eye and your mind to know what you want from an image -- you also have to have an understanding of ISO, aperture/DOF and shutter speed
I use M quite a bit if I am shooting when the lighting doesnt change and/or the model doesn't move --- theatre with fixed lighting is one example
also, in tricky situations when the camera just can't get it right, I use M or I use Av/Tv/P with the * button for selective/partial exposure
if things need to be quick and lighting might change, M is only really an option for the very quick, otherwise things can go awfully wrong, as I have learnt ... but the more you use M the more it becomes 2nd nature to compensate for changing conditions, neverthess, you can never be as quick as the camera!
one thing M does offer is consistancy. when shooting in other modes it is easy for the camera to change the exposure if you point at a slighty lighter/darker area -- with M is stays fixed, so all your shots have exactly the same exposure, which can be useful if you have the exposure right!
another thing I use M for is flash photography: I tend to expose for the highlights (bright sky for example, ie. make sure it is "correctly" exposed) and then use the flash to fill the shadows
one more thing, is night photography and long exposures: here M is a must
I still havent answered you question, and so really you need to try it out.
go to M and fill some CF cards with experiments, learn to use the trio of variables: ISO, aperture and shutterspeed, as well as working out metering (the * is a great help)
if you want to get into technicalities, ansel adams is a great place to start, as his ZONE system is useful in understanding how to see light and place it on film (obviously we have to appy this to digital, and there are differences, but a sound grounding nevertheless)
--
AJ
http://www.pbase.com/manjade