You don't want to cache the XML document. It would be better to read/parse it into a "configuration" object. Depending on how complex or simple your configuration is, it could be a simple Map or something more complex.
One benefit (beyond the concurrency problems from parsing the same doc from multiple threads) is that you are not tied to the XML format for your configuration. Think about how all configs used to be in properties files, then XML came about and every open source package added support for XML. Then annotations came, and that was supported then too. Hibernate is a good example of that.
What you want to do is parse your config file and keep the resulting configuration object in your cache instead of the source XML.