I think, Win32::Process just helps you if you've started this Process with Win32::Process...

For fetching Win32-Processes, there are several possibilities, e.g.

#!perl -w
use strict;
use Win32::OLE qw(in);

#Mode: Window Management Instrumentation (WMI)

# processproperties
my @properties = qw(Caption CreationClassName CreationDate CSCreationC
+lassName
            CSName Description ExecutablePath ExecutionState Handle
            HandleCount InstallDate KernelModeTime MaximumWorkingSetSi
+ze
            MinimumWorkingSetSize Name OSCreationClassName OSName
            OtherOperationCount OtherTransferCount PageFaults PageFile
+Usage
            ParentProcessId PeakPageFileUsage PeakVirtualSize PeakWork
+ingSetSize
            Priority PrivatePageCount ProcessId QuotaNonPagedPoolUsage
            QuotaPagedPoolUsage QuotaPeakNonPagedPoolUsage QuotaPeakPa
+gedPoolUsage
            ReadOperationCount ReadTransferCount SessionId Status Term
+inationDate
            ThreadCount UserModeTime VirtualSize WindowsVersion Workin
+gSetSize
            WriteOperationCount WriteTransferCount);

# processmethods
my @methods = qw(Create Terminate GetOwner GetOwnerSid);

my $server = ''; # local machine

my $locatorObj = Win32::OLE->new('WbemScripting.SWbemLocator')
    or die ("Error in creating locator object: ".Win32::OLE->LastError
+()."\n");

$locatorObj->{Security_}->{impersonationlevel} = 3;

my $serverObj = $locatorObj->ConnectServer($server, 'root\cimv2')
    or die ("Error in creating server object: ".Win32::OLE->LastError(
+)."\n");

my $procSchema = $serverObj->Get('Win32_Process');

#@properties = map{ $_->{Name} } (in $procSchema->{Properties_});
#@methods    = map{ $_->{Name} } (in $procSchema->{Methods_});

foreach my $process (in $serverObj->InstancesOf("Win32_Process")){
    foreach (@properties){
    printf ("'%20s' => '%s'\n", $_, $process->{$_} || '' );
    }
    print ("-----------------------------------------------\n");
}
[download]

or use: tlist.exe or pstat.exe from WinNT-Reskit

Best regards,
perl -le "s==*F=e=>y~\*martinF~stronat~=>s~[^\w]~~g=>chop,print"