I still think that using a regex to break the data up into the two parts you want,
and catching them in a hash, is the easiest way to achieve what you are asking for.

Orig regex beefed up slightly.

#!/usr/local/bin/perl -w
use strict;

use Data::Dumper;

my %names_emails = map { /^(?:To|From|Reply-To): (\S+)\s+<?([^\s>]+)/ 
+} <DATA>;

print Dumper( \%names_emails );


__DATA__
To: Bob <test@spam.com>
From: lucy test@wherever.c0m
Reply-To: somebody somebody@spam.com
To: Bob2 <test2@spam.com>
[download]

Output:

:!./test.pl
$VAR1 = {
          'somebody' => 'somebody@spam.com',
          'lucy' => 'test@wherever.c0m',
          'Bob2' => 'test2@spam.com',
          'Bob' => 'test@spam.com'
        };
[download]

Disagree? Am I missing what you are looking for?