Having done a lot of Windows help in the last time I learned some important things. The first thing is that people don't care which Browser or Email client they use if it is installed on their Computer. I usually remove IE and Outlook (as far as possible) and then install Firefox and Thunderbird. I tell the people it's more secure and they start using it on the fly. They just don't care and I feel better
Another thing I learned is that there is far more software I'm used to use available on Windows than I thought. For example I didn't know that there is a Gimp port to Win32 and even Frozen Bubble is available. It's the best way to get people in touch with Free Software just to install it on their favorite OS.
The last thing even I always run into and Linux newbies tend to run in is that they know an application on windows and look for something that gives them the same functionality on Linux. I did some google research today but I didn't find something that I could imagine usefull regarding that case.
What I would propose is a free software library that gives the people to search for applications by "Windows Name". For example I kept looking for a good application that is similar to Dreamweaver on Windows. Nvu is the answer, a project started by the Lindows people. It took me a good amount of time just finding this project. Sourceforge and Freshmeat are good for what they do, but actually we need something that gives people a hand for finding what they need by their own means. One could even add something like windows ports and i18n stuff in order to make people test something on Windows knowing that it exists on Linux too. If the people are used to the applications, the OS doesn't matter.
Maybe I'll start doing something in that direction, but only after finishing my exams, doing another talk and write two articles I was asked to do.