Were I to hazard a guess, I would say it is the fact that the Windows CMD prompt does not understand '/' as a path separator; instead, it uses '\' (which most things with a *nix background -- including C and perl -- use as an escape character). In order to include a '\' in a string, you would need to use "\\", or a '\' in a single-quoted string. You can also use the q or qq operators as a way to quote the string. ('q//' is a way to represent a single-quoted string, and 'qq//' a double-quoted string.)
# Replace assignment with this.
# 'q//' treats as a single-quoted string, which does not try to
# interpolate characters. As a result, the double-quotes in
# the command do not require escaping. Here I used the '/' as
# the delimiter for the single-quoting 'q', but could be other
# characters depending on what is needed in the string. I also
# used the '.' to concatenate the string, allowing it to be
# written across multiple lines so the spaces between parameters
# were obvious.
my $cmd = q/fsutil/ # command
. q/ /
. q/file/ # parameter 1
. q/ /
. q/setShortName/ # parameter 2
. q/ /
. q/"C:\Users\James\Music\國語懷念&#
+32769;歌 Vol. 2"/ # parameter 3
. q/ /
. q/"Vol2~00A"/; # parameter 4
# The double-quotes in parameter 3 are necessary
# due to the spaces within the file name.
# Continue remainder of code as before
Hope that helps.