Win32::AdminMisc and heres some code to get you started..

#! perl.exe

use strict;
use warnings;

use Win32::AdminMisc;

my (@users, @groups);

print "List of USERS\n";
Win32::AdminMisc::GetUsers("","",\@users);

foreach my $usr(@users) {
    print "$usr\n";
}

print "\nList of GLOBAL Groups\n";
Win32::AdminMisc::GetGroups("",GROUP_TYPE_GLOBAL,\@groups);

foreach my $grp(@groups) {
    print "$grp\n";
}
[download]

Update: I have also had some good success with Win32::NetAdmin although can't remember if I got the password stuff working..