I presumed that editing gtk themes (thats what xfce4/xfwm4 uses) would be a total PITA. It wasn't. Infact it was so simple I'm concidering starting to make my own... Could be really interesting and add something back to the community.
So this is how :
# make a copy of the theme your editing - "Just in case"
cp ./Xfce4-dusk ./Xfce4-dusk-edited-by-smiley
# I use nano - you may prefer vi/ed/something else...
sudo nano -w ./Xfce4-dusk-edited-by-smiley/gtk-2.0/gtkrc
Now, for something simple like a window border you are looking for:
# This is for the window borders (xfwm4 & metacity)
bg[SELECTED] = "#D55C00"
fg[SELECTED] = "#ffffff"
bg[INSENSITIVE] = "#A14600"
fg[INSENSITIVE] = "#DC894A"
Where bg[SELECTED] is the hex colour code for the border of the selected window, fg[SELECTED] is the hex colour of the text of the title bar.
Simularly bg[INSENSTIVE] is the border colour of a non-selected window, which is generally a darker colour to indicate the non-active status of this and fg[INSENSTIVE] is the text colour of the title bar when that window is inactive.
Once you've edited this, simply change your theme via the appearance settings of your window manage/desktop enviroment - for Xfce4 this is via settings -> appearance. Select your new theme and happy days :)
## WARNING - I'm not sure what'd happen if you edit themes in place while being used. They may update the wm "live" or it might explode in your face. :)
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