Due to a rather intense dislike of both Unity and Gnome-Shell in their current iterations, I've recently switched to using Xubuntu. One quibble i've had is that changing the theme in xfce4-settings-manager often causes the theme used with gtk3 applications to revert to the ugly default, presumably as many themes do not have gtk3 counterparts to display.
The only solution i've been able to find with regards to manually changing the gtk3 theme is to hunt down the theme folder in /user/share/themes and copy the gtk-3.0 folder from that theme into ~/.config.
So if you've changed the theme and just want the default greybird gtk-3.0 theme back for your gtk3 apps, while keeping a different theme for your gtk2 applications you might run something along the lines of:
cp -r /usr/share/themes/greybird/gtk-3.0 ~/.config
For applications run as root to adapt to this theme too you'll need to copy to /root/.config also.
sudo cp -r /usr/share/themes/greybird/gtk-3.0 /root/.config
Hope that helps someone, as it was beginning to annoy me rather a lot. If anyone has a cleaner way to do this please let me know.