I think it's safe to assume each host is there just once so it may be better to use ForceArray => ['process'] Which will somewhat simplify the code:

#!/usr/bin/perl -w
use strict;
use XML::Simple;

my $parser = new XML::Simple(ForceArray => ['process']);
my $ref = $parser->XMLin('c:\temp\file.xml');
foreach my $host (keys(%$ref)){
  foreach my $proc (keys(%{$ref->{$host}->{process}})){
    print "$proc is running on $host\n";
  }
}
[download]

Also it may be better to use each() instead of foreach():

#!/usr/bin/perl -w
use strict;
use XML::Simple;

my $parser = new XML::Simple(ForceArray => ['process']);
my $ref = $parser->XMLin('c:\temp\file.xml');
while (my ($host, $processes) = each %$ref){
  foreach my $proc (keys(%{$processes->{process}})){
    print "$proc is running on $host\n";
  }
}
[download]

Or using a different module:

use XML::Rules;
my $parser = XML::Rules->new(
    rules => {
        process => sub { '@list' => $_[1]->{name}},
        _default => sub { $_[0] => $_[1]->{list}},
        config => 'pass no content',
    }
);
my $data = $parser->parse(\*DATA);
#use Data::Dumper;
#print Dumper($data);

foreach my $host (sort keys %$data) {
    foreach my $proc (@{$data->{$host}}) {
        print "$host runs $proc\n";
    }
}

__DATA__
<?xml version="1.0" encoding="utf-8"?>
<config>
...
[download]

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