You should declare the namespace prefix using an XmlNamespaceManager
before you can use it in XPath expressions.
XmlDocument doc = new XmlDocument ();
doc.Load("/Users/buttercup/Projects/23564466/kram.xml");
XmlNamespaceManager nmspc = new XmlNamespaceManager(doc.NameTable);
nmspc.AddNamespace("form", "http://www.example.com/file.xsd");
nmspc.AddNamespace("addData", "http://www.example.com/file2.xsd");
nmspc.AddNamespace("_colored", "http://www.example.com/colored.xsd");
string fieldValue = doc.SelectSingleNode("/form:Documents/_colored:_colored/_colored/_Field1", nmspc).InnerText;
http://msdn.microsoft.com/en-us/library/system.xml.xmlnamespacemanager.aspx