To eyecandy your XFCE desktop, you can get the theme on XFCE-look.org sites, there are lot of theme, icon, etc. Before that, you must create .themes folder on your home desktop first.
$mkdir ~/.themes
1. Installing & Setup Themes on XFCE
To Start set up theme. Find Themes on xfce-look.org, for this example, i will apply this themes:
http://xfce-look.org/content/show.php/Ambiance+Crunchy?content=151180
Download the themes, then extract it:
There are two items, icon & themes,copy any folder inside themes into .themes like this picture.
And for the icons, copy folder inside icons to /usr/share/icons, but on this themes the icons is useless, just skip it.
Then open Start Menu -> Settings -> Appearance, Now the themes is added.
Click to apply.
2. Installing Icons on XFCE
Here's the list icon that you can install (available on official repo)
And from AUR:
If you get from other sources, simply copy folder icons into /usr/share/icons,
Then open Settings Appearance, then choose Icons Tab, then set your icons.
3. Change Fonts
open settings -> appearance ->Fonts Tab, then set your prefered fonts.
4. Change Window Manager
Open Settings -> Window Manager -> Style Tab
To install new window manager, same as installing themes, copy folder of wm themes, into .themes folder.
5. Change Mouse Cursor
Open -> Settings -> Mouse & Touchpad -> Theme Tab
For more cursor themes, search on PacmanXG4.
6. Change Windows list / buttons on Panel looks Win 7 Style.
Right click on panel, then panel, -> Panel preferences > Items Tab, choose windows buttons. then edit. Uncheck Show Button Labels
Then your windows button will like this:
Ok that's about appearance on XFCE.
Enjoy.