Reading the XML::Simple man page helps. Write your expected xml to a file, say, foo.xml, then read and dump it with a script named foo:

use XML::Simple;
use Data::Dumper;
$Data::Dumper::Indent = 1;
my $config = XMLin();
print Dumper($config);
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Voilà:

$VAR1 = {
  'Node' => [
    {
      'Type' => 'Module',
      'No' => '1',
      'File' => 'Sample1.pl',
      'Description' => {},
      'Label' => 'AA'
    },
    {
      'Type' => 'Methods',
      'No' => '2',
      'File' => 'Sample1.pl',
      'Description' => 'Initiator',
      'Label' => 'BB'
    },
    {
      'Value' => [
        {
          'No' => '1',
          'content' => 'Ignore'
        },
        {
          'No' => '2',
          'content' => 'Retry'
        },
        {
          'No' => '3',
          'content' => 'Abort'
        }
      ],
      'Type' => 'Methods',
      'No' => '3',
      'File' => 'Sample2.pl',
      'Description' => 'Destructor',
      'Label' => 'CC'
    }
  ]
};
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Lather, rinse, repeat.

_($_=" "x(1<<5)."?\n".q·/)Oo.  G°\        /
                              /\_¯/(q    /
----------------------------  \__(m.====·.(_("always off the crowd"))."·
");sub _{s./.($e="'Itrs `mnsgdq Gdbj O`qkdq")=~y/"-y/#-z/;$e.e && print}