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Two ways including many to work with xna xml would be:
1) REFERENCE TO USE: Provides
Methods for reading and writing XML XNA intermediate format.
Namespace: Microsoft.Xna.Framework.Content.Pipeline.Serialization.Intermediate
Assembly: Microsoft.Xna.Framework.Content.Pipeline (in microsoft.xna.framework.content.pipeline.dll)

This enables IntermediateSerializer class which is part of the XNA content pipeline.
In comments read on several pag. with DA XBOX360 PC ERROR wrong. While msdn says it works with xbox360 error has been reported. Link to MSDN


2) FOR USE ON XBOX is preferred. NET XML (XmlReader, XmlWriter, XmlDocument, XmlSerializer, etc). They
available on the Xbox, and PC is going well too. OSEA
the System.Xml;

deserialization leave an example, take data from an XML file and XNA draws them. Something interesting is the use of ColorConverter , to convert a string in color.

EXAMPLE FOR DOWNLOAD