How to print Array values of custom Fields Meta?

Based on the screenshot I assumed is var_dump of your $item
The code should look like

<?php $item = get_post_meta($post->ID, 'occupationalCategory', false); ?>
<?php print_r( $item['occupationalCategory'][0] ); ?>;
<?php print_r( $item['occupationalCategory'][1] ); ?>

$item contains array, with a element which key is ‘occupationalCategory’, this element points to other array with two elements