Yep it's entirely possible to do what you suggest. Here's the data structure that XML::Simple would create (results dumped via Data::Dumper):

$VAR1 = {
          'ZIP_PATH' => 'p:\\',
          'LOCAL_PATH' => 'd:\\pb8\\',
          'SYSTEMS' => {
                         'Treasurer' => '1.5.200',
                         'Assessor' => '1.5.499'
                       }
        };
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And then:

my $config = read_ini("AppDeployment.xml");
my $assessor_version = $config->{SYSTEMS}->{Assessor};
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-- vek --