kill works for processes outside of Perl as well on Win32.

... for a very limited definition of "works". You can use kill to terminate other processes, but you can't send them signals, because Windows doesn't implement signals.

Inside a perl.exe process that pseudo-fork()ed a child-pseudo-process, signals may work, but not outside that process.

Simple example:

killme.pl

#!perl

use strict;
use warnings;

$SIG{'HUP'}=sub {
    print "Got a HUP signal\n";
};
$SIG{'TERM'}=sub {
    print "Got a TERM signal\n";
};

open my $f,'>','pid.txt' or die "Could not write pid.txt: $!";
print $f "$$\n";
close $f;

$|=1;
print "Waiting to be killed\n";
while (1) {
    print '.';
    sleep 30;
}
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killer.pl:

#!perl

use warnings;
use strict;

open my $f,'<','pid.txt' or die "Start killme.pl first";
my $pid=<$f>;
close $f;

for my $sig (qw( HUP TERM KILL )) {
    print "Sending $sig ...\n";
    kill($sig,$pid);
    sleep 2;
}
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Open two terminals on a Linux system, start both scripts (killme.pl first), and you see this:

/home/foken>perl killme.pl
Waiting to be killed
.Got a HUP signal
.Got a TERM signal
.Killed

/home/foken>
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/home/foken>perl killer.pl
Sending HUP ...
Sending TERM ...
Sending KILL ...

/home/foken>
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Open two command shells on Windows, start both scripts (again killme.pl first) and you see this:

F:\>perl killme.pl
Waiting to be killed
.
F:\>
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F:\>perl killer.pl
Sending HUP ...
Sending TERM ...
Sending KILL ...

F:\>
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Note that sending HUP terminated killme.pl, completely ignoring the fact that it has set up a HUP signal handler.

One could argue that Windows has no HUP signal, so let's remove the relevant code parts and watch again:

F:\>perl killme.pl
Waiting to be killed
.
F:\>
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F:\>perl killer.pl
Sending TERM ...
Sending KILL ...

F:\>
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Ooops, death by SIGTERM, again ignoring the signal handler inside killme.pl.

Alexander