I prefer XML config files over binary files. At least, XML is human readable.
That's comparing apples with oranges. Sounds a bit to me like a desperate defence of some one used to work on projects having XML for config files while at the same time deep down feels this was not the best decision made.
For the same reason I could say, 'I prefer binary over encrypted files I don't have the key for. At least you can get anything useful out of it at all.' All have to admit: That's true. But it's pointless.
But back to OP's topic:
However some one may sees it about config made in XML, as I already said, I see it way too much effort messing with those.
you may ask yourself if you can live with xfce (or any other DE) as it come, or not.
Several years ago I was at likewise crossroads. After switching from Windows, which GUIs I all always hated was one of the core reasons to turn my back on it, to FreeBSD, switching from LXDE to xfce (I never really used Gnome, or KDE - simply not my style) I finally realized I don't even want a Desktop Environment at all. DEs are turn-key GUIs. Turn-key means predefined, almost never configurable to the last detail. Of course, not. You either chose something predefined, and live with it, or start to config it all over by yourself anyway. One can be fully satisfied with that, of course. But if you want to configure more than change of wallpapers, or window's decor color - yeah, yeah, I'm not fair, I know; beancounters don't eat me alive for that simplification - you'd be better recommended with a (pure, simple) window manager.
Browse a bit and pick one you may configure
everything - within textfiles, not XML. There are several. Learn how to config it, and "tailor your own, personal DE." That's what they are for.
As I already said, in the beginning it's a bit effort, but in the long term some one who tried several DEs but still hasn't found what she or he's looking for might be more satisfied that way.
For myself I am at crossroads again.
Since I'm asking myself why to use resize- and movable, decorated windows at all, by default leaving large parts of the monitor unused while I always prefer the usage of full- or at least splitted screens. So I'm checking if I switch to a tiling WM like
i3,
spectrwm,
herbstluftwm, or
dwm (which can do both modes)
But that's just as ideas
if you consider to look for something else.
Again:
If you can be fully satisfied with xfce, and one can, there's no reason to change.