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Net::Cmd->code()
Net::Cmd->message()

# Create ourselves an SMTP object
my $smtp = Net::SMTP->new(
...
$smtp->to("youthere\@mailserver.de")
   or die "Error on RCPT TO: ", $smtp->code(), " ", $smtp->message();
$smtp->quit;

$smtp->mail("postmaster\@mailserver.co.za", Size => 52428800);
if ( $smtp->status() =~ /^[45]$/ ) {
   # informative error here
   exit(1);
}

if ( $smtp->status() =~ /^[45]$/ ) {
   if ( $smtp->message() eq "size limit exceeded" ) {
...
      print "The message is too big. Boo-hoo\n";
   }
}