According to the schema structure you showed, there should be no namespace prefix for tblStaff. That would make your selection as follows:
thisXDocument.DOM.selectSingleNode("//dfs:myFields/dfs:dataFields/tblStaff/@Designation").text
But if this doesn't work, then I suspect that there is a different namespace being used. You will need to find out what it is: (ns1:tblStaff, or something like that).