Well I am not sure I understand your question and it has been a while since I used PHP but is this what your looking for.
for associative array of associative arrays.
$container = array('country' => array('US' => 'United States'));
$container['country']['UN'] = 'United Nations';
$container['country']['PH'] = 'Philippines';
echo $container['country']['US'];
echo $container['country']['UN'];
echo $container['country']['PH'];
for single associative array
$countries = array('UN' => 'United Nations');
$countries['US'] = 'United States';
$countries['PH'] = 'Philippines';
echo $countries['UN'];
echo $countries['US'];
echo $countries['PH'];
EDIT: you could even get crazy if you wanted and do something like this. :)
$countries = array('UN' => 'United Nations');
$countries['US'] = 'United States';
$countries['PH'] = 'Philippines';
$countries['other_countries'] = array('PL' => 'Poland');
$countries['other_countries']['RO'] = 'Romania';
echo $countries['UN'];
echo $countries['US'];
echo $countries['PH'];
echo $countries['other_countries']['PL'];
echo $countries['other_countries']['RO'];