For adding add custom button to backend order table you can use this code
add_action( 'woocommerce_admin_order_actions_end', 'add_content_to_wcactions_column' );
function add_content_to_wcactions_column() {
// create some tooltip text to show on hover
$tooltip = __('Some tooltip text here.', 'textdomain');
// create a button label
$label = __('Label', 'textdomain');
echo '<a class="button tips custom-class" href="#" data-tip="'.$tooltip.'">'.$label.'</a>';
}