I used to do quite a bit of Tcl programming back in the mid to late 1990s. I've since largely dropped it, but Tcl still is used quite a bit in specialized use cases.
To use Tcl with XML, it seems like the most popular solution is the TclXML package :
http://tclxml.sourceforge.net
From what I can tell, it's the best / only package for XML in Tcl, although here's a 11-year old article by Steve Ball which seems to reference other approaches :
http://www.usenix.org/events/tcl98/tcl98/full_papers/ball/ball.pdf