\documentclass{book}
\usepackage{url}
\begin{document}
\urldef{\PSPpath}{\path}{E:\MP_ROOT\100MNV01}
\urldef{\psppath}{\url}{E:\MP_ROOT\100MNV01}
First I use an explicit call: \path{E:\MP_ROOT\100MNV01}, then I use
the command: \PSPpath.
First I use an explicit call: \url{E:\MP_ROOT\100MNV01}, then I use
the command: \psppath.
\end{document}