I started XML by grabbing a book and read.
Then I grabbed an XML file and XMLSpy and played with it. I messed stuff up, then looked up as to why I was getting "not a valid XML File" error. Learned about DTDs, etc.
I would suggest first understand the fundamentals of XML. It's a similar structure to HTML in that it uses <> style tags, but nothing more.
Unlike HTML, XML doesn't have a set tag set.
Think of XML files as a really fancy windows INI file. They do the complete exact same thing, but XML just displays it different, putting it all in a hierarchy, makeing it easier to read and easier to parse.
That's it .. There are other things to XML, like DTD, data type definition, and Schema files. They are used to define an XML document. Make sure it's "valid" before a program trys to read it and die horriably cause of false formats.
Next step is to play with it. Open a file, make a BIG change, like change the Length of 23 to 400. Or the size from 10x30 to 323x492 and see what happens.
Change a name from 'Target' to '*(#&#*# TARGET #$($@(@' or something. Something nice and big so you can easily spot the changes. Then you'll see.
Oh, also - I find printing out files seems to help as well. Easier to look at things on a hard sheet of paper then trying to grasp it on the computer screen. Some can do that, others can't.