1. Install necessary firmware
Debian doesn't come with non-free firmware installed by default. On booting after installation, I noticed some warnings about firmware not found. Enabling the non-free repository and installing the firmware-linux package and its dependency firmware-linux-nonfree got my graphics card (such as it is) working.
2. Put a volume control icon in the panel
I don't know why this isn't there by default, but it's easy to rectify: right click on the panel, select Panel and then Add New Items, and add the Mixer. Click on it and then on Select Controls. Tick Master or PCM- whichever works best for you.
3. Sort out screensaver and power management
XFCE in Debian Wheezy comes with two applications capable on controlling power management, which can result in some perplexing behaviour.
- The screensaver comes on, but the screen doesn't shut down after the set period.
- The screen blanks, but the backlight stays on, leaving a ghostly illumination.
- VLC is set to disable power management, but the screen blanks 10 minutes into a video.
Confused? You should be!
There's more. A random screensaver is enabled by default, but not all of the screensavers selected are installed, meaning that sometimes a screensaver will start, some times the screen will blank.
Practically, if you want to use a screensaver, enable power management in Screensaver (note that all three settings, Standby, Suspend and Off are the same- this sems to be fine for a laptop anyway) and make sure the On AC > Monitor > Put display to sleep when computer is inactive for: value is greater than that set in Screensaver.
[Update: although this originally worked for me, my screen started going blank while watching videos again a few days ago. I don't know why, because the settings seem to be the same and I haven't had this problem for months. Setting the XFCE Power Manager slider to Never seems to have fixed it. Not sure why I didn't do that in the first place.]
If you don't use a screensaver, Power Manager Monitor settings can be used to shut down the screen.
4. Create some special folders icons for the Tango icon theme
Tango is the default icon theme for XFCE, yet it has a very annoying bug: it has no icons for special folders in the home directory, meaning that these folders are displayed with an icon from the Gnome icon set. You can of course use another icon set that does include special folder icons, but I rather like Tango. The only solution I have found is to copy the default folder in the Tango theme and rename it for all the special folders. (Well, actually creating symlinks would be a more elegant solution, come to think of it...) You can see what I've done in this screenshot.
Of course what is really needed is for somebody to produce some special folder icons for Tango...
[Update: if changes don't take effect, update the icon cache,
gtk-update-icon-cache /path/to/theme/directory/as described on XFCE Docs.]
5. Enable anti-aliasing
If fonts look bitty, go to Settings > Appearance > Fonts and enable anti-aliasing. Experiment with the level of hinting for the best appearance.
[Update: also see this post on enabling LCD hinting (it's not a GUI option).]
6. Enable the compositor
Go to Settings > Window Manager Tweaks to enable compositing. XFCE has its own fairly minimal compositor. It provides windows shadows and transparency, and will enable docks that require compositing to run.
Although the compositor on XFCE is very minimal, I found that video lagged severely with compositing enabled on this laptop. Watch out for this issue on older hardware (10 years in this case).
7. Enable multimedia
Enabling multimedia in Debian used to be a big issue, but not any more. Debian now has multimedia support. Wheezy plays my music and video files out of the box. There are only a couple of things to mention here.
Install flashplugin-nonfree if you want to view Flash content on web pages.
To enable DVD playback, download and install libdvdcss2 as described on debian.org.
8. Install a nice theme
Debian doesn't pay any attention to making XFCE look nice, but XFCE itself is very customisable. xfce-look.org has lots of themes. Themes need to be set in Appearance and Window Manager. Themes can be placed in /home/user/.themes, but for system applications like Synaptic, they need to be in usr/share/themes. Some themes may require additional engines to display correctly. GTK3 applications like Network Manager will require GTK3 support to display correctly.
Here's my own desktop. Keeping it minimal, this theme doesn't require additional engines. Its a modification of the Axiom theme with added GTK3 support. The icon theme is Tango, but with panel icons from the Elementary icon theme.
9. Enable the Print Screen button
The prt sc button is not enabled by default. The excellent ArchLinux XFCE Wiki describes how to enable it. Add the command as described then press the prt sc key to bind it to that key.
10. Enable quick search in Synaptic
Install apt-xapian-index. Building and rebuilding the index may take some CPU time, but will speed up searches.