A couple of ways..
favorites
go to c:
- documents and settings
- (user/log on / account name)
- Favorites folder in here (drag and drop it onto an external or USB drive or whatever medium
on the new pc drop the favorites folder into the appropriate folder (vista is about the same place windows 7 not sure)
i tend to organize my favorites folders from here as it's easier and quicker.
ourlook express not sure about but for outlook search for "*.pst" files it'll give you the outlook folder, drop that whole folder onto your usb/ external drive and on your new, after installing outlook replace the pst files with the ones from your old computer and you wil lhave the email archive.
essentially in outlook, the emails are stored in a .pst file for each account so copying that pst folder over will give you all your archived emails. (i have all my business ones archived since 2003) also i have a program called genie outlook back up manager which allows you to back up and reinstall outlook and all settings (across to a new pc too)