XFCE shares the same desktop paradigm as Windows XP (panel, menus, window buttons etc), so it's an easy switch to make, except for a few annoyances which may put off new users. I'm going to detail theses annoyances and how to get round them here.
Problem panels
After installing XFCE and logging in to your account, you are prompted to set up a panel. However, if you don't save the session after logging off, the next time you log on, you will not see any panels. You can get them back by right clicking on the desktop and going to Applications>Settings>Panel. However, you may see a popup window with the following error message as described on the Arch Linux forum:
The panel cannot be edited while running in kiosk mode.Solution: Drop out of XFCE with Ctrl + Alt + F1, navigated to ~/.cache/sessions/ and delete the contents with the following command:
rm -rf *Restart, log in to XFCE, set up panels as required and save the session on exit to see your panels appear at next log on.
Unwanted saved sessions
Having saved your session to save your panels, you may decide that you don't want to have every application you had open at shutdown reappear when you next log on. The solution to this is to close all applications, log off saving the minimal session, log back on and disable saved sessions.
However, you may be puzzled to find that applications are still reopening at logon.
Solution: be aware that only the logout GUI respects the preference to not save sessions. (See this post on the XFCE forum.) The Action Buttons panel plugin seems to use a shutdown method that does not respect session preferences, so if you're wondering why applications autostart when you've chosen not to autosave sessions, Action Buttons may be the culprit.