Could this be done using GetOpt? or @ARGV? Any help would be much appreciated

Very simply:

foreach $item(@ARGV){
print $item,"\n";
}
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When I run that code with:

C:\Documents and Settings\Administrator\My Documents>foo.pl "c:\Docume
+nts and Settings\Administrator\My Documents"
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I very predictably get:

c:\Documents and Settings\Administrator\My Documents
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Remove the bounding quotes and I get

c:\Documents
and
Settings\Administrator\My
Documents
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Why? Very simple: your (or Microsoft's shell more correctly) interprets the spaces and feeds things separated by spaces as separate arguments. If your script is to deal with that then it is up to you as a programmer to deal with that.