Let's consider this XML where there are two (or more) identicals keys (name).

<acme>
  <name role="main">Bugs Bunny</character>
  <name role="support">Elmer Fudd</character>
</acme>

Data::Dumper can be used to understand how XML::Simple is interpreting the XML.

#!/usr/bin/perl
use strict;
use warnings;
use XML::Simple;
use Data::Dumper;

my $xml= XMLin("example.xml");
print Dumper $xml;

Which will produce the following.

• Data inside of { } is interpreted as a hash
• Data inside of [ ] is interpreted as an array
• "name" is the root key
• "content" and "role" are child keys in an array below the root key
• "Bugs Bunny" and "Elmer Fudd" are values of the "content" key
• "main" and "support" are values of the "role" key 

$VAR1 = {
          'name' => [
                    {
                     'content' => 'Bugs Bunny',
                     'role' => 'main'
                    },
                     'content' => 'Elmer Fudd',
                     'role' => 'support'
                    }
                  ]
        };

The following . . .

#!/usr/bin/perl

use strict;
use warnings;
use XML::Simple;

my $xml = XMLin("example.xml");

print $xml->{'name'}->{'content'};

. . . will return this output.

Not a HASH reference

This is because the XML contains an array. In the following, . . . 

print $xml->{'name'}->[0]->{'content'};
print $xml->{'name'}->[1]->{'content'};

[0] will return "Bugs Bunny" and [1] will return "Elmer Fudd".

Bugs Bunny
Elmer Fudd

Or you can loop through the <name> key, which will cause $key variable to contain [0] and [1]. The following will also return both "Bugs Bunny" and "Elmer Fudd".

foreach my $key ( keys @{$xml->{'name'}} ) {
  print "$xml->{'name'}->[$key]->{'content'}\n";
}