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If you want to change it system-wide, you can't do it because many programs save it in their own folder by default. You can move My Documents folder to another location by right clicking and choosing properties.
As far as changing default location, some programs give you the option, in others choose Save As and save it where you want and it sticks the next time. You have to try all these ways.
I know that in some tweak programs, like tweakXP, you can change registry settings to achieve what you want but even then you can't do it globally because different programs have different default save locations.
For example, most microsoft products will save in My Documents but Lotus will save in the Lotus Folder.
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