The uses clause in Delphi refers to Delphi units, either compiled in a *.dcu file or a *.pas source file that the compiler will use to generate the corresponding *.dcu that is needed.
You cannot just reference the DLL itself.
To use your DLL, you would need at least a unit that would expose in a Pascal way the DLL interface or parts of it.
It can be the Pascal translation of a C header file or just declaring some external routines from the dll to load statically with your program...
What you probably need to reference to work with XML in Delphi are XMLIntf and maybe xmldom.
Have you looked at what the XML Data binding wizard or the XML Mapper Tool can do for you?
Note: I assumed you were working with Delphi Win32. And AFAIK system.xml.dll is part of the .NET world.