Refering to form API Drupal 7 for #value
$form['field_a']['und']['#value']
Used by: button, hidden, image_button, submit, token, value
Description: Used to set values that cannot be edited by the user.
For $form_state['values']['field_a']['und'][0]['value']
$form_state is one of the arguments passed to a form submission
handler, or a form validation handler; its main usage is to retrieve
the values entered from the user in the form see the content of
$form_state['values'])
So you should use $form_state['values']['field_a']['und'][0]['value']