Phil Windley recently discussed the difficulty of moving to open source software in government offices. The biggest factor, he stated, was training users. While there may be issues I’m not aware of, my experience has shown that someone who uses Word can use Open Office without any additional training. The same goes for Windows users on a preconfigured Linux desktop (especially KDE).
My parents, who are not particularly experienced with computers, were able to use Mandrake without much difficulty. Their biggest complaint was having difficulty reading Word documents. They could check their email, browse the web and use a word processor and I would estimate that those three activities fulfill 90% of the typical user’s needs.
If you were to give a user a preconfigured Windows machine and a preconfigured Linux machine, I doubt there would be much difference in their ability to use it. The only difference would probably be the length of time they could stay on without crashing.