WP_Query of custom post type sorted by meta_key has unexpected results

I think the issue is that it’s being interpreted as a STRING type and being ordered character by character. Maybe try turning this into a meta query and forcing the DATETIME type like the example shown below:

'meta_query' => array(
    'starttime' => array(
        'key'   => 'start_time',
        'type'  => 'DATETIME',
    )
),
'orderby' => array( 'starttime' => 'ASC' ),

See WP_Query Custom Field Parameters

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