Icon text is one of the few elements that you cannot edit from the desktop in Xfce. However, according to a Readme file from the site, you can quickly customize it by editing the .gtkrc-2.0 file in your home directory, so that it reads something like this:
The first stanza sets the transparency of the highlighted background of the text, using a value from 0 (for no transparency) to 255 (total transparency). The next three lines define the background color, and are irrelevant if you set the transparency to 0. The third set of three lines sets the color for the text itself.
You can set the color for both the background and text for when the icon is not selected (Normal), for when the icon is selected but not activated (Selected), and for when you have opened the icon (Active). For each entry, color is defined using standard Web colors.
Once you have set the colors, save the file and log out of Xfce and log back in again to have your changes take effect.
Xfce generally comes with a standard, accordion-style menu. If you want to simplify the menu, or if a program doesn't automatically add an item to the menu system, then you can go to Settings -> Menu Editor to make modifications. Adding items is similar to adding an icon to either the desktop or the panel, while deleting one is a matter of selecting Remove entry from the right-click menu.
Clipman is Xfce's answer to KDE's Klipper -- a multiple clipboard that allows you to copy multiple items, then select which one to paste. Among other options, you can configure how many items to save at one time, and whether the clipboard is emptied when you exit Xfce. If you like having a multiple clipboard in MS Word, you'll like having one for the entire desktop even better.
In addition to supporting multiple workspaces, Xfce also gives you the option of creating different user profiles for your desktop as you log in. For instance, if you choose, you could have desktops with different sets of icons for programming and for office productivity. By setting up different sessions, instead of different workspaces, you can use less memory.
To enable multiple sessions, go to Settings -> Session and Startup -> General, and check the box beside Display chooser on login.
Thunar, Xfce's file manager, superficially resembles GNOME's Nautilus. However, any prolonged use of Thunar will soon dispel any notion that it is similar to Nautilus. For one thing, although Thunar has fewer customization options and cannot be used to burn DVDs, it is considerably faster than Nautilus. It also has some small but useful innovations such as displaying the Trash in the directory tree, allowing custom actions to be set when particular types of files are opened, and defaulting to the last directory viewed, instead of the home directory.
In addition, Thunar has a separate view called Bulk Rename, which is available from the Systems sub-menu of the main menu. Bulk Rename allows you to change not only the names, but also the other attributes of the files you select, a feature that is handy when you are ripping CDs and want to indicate the album on individual song files or when you want all the files in a project to have related names.