I have identified a method to combine the APPS25 code and the £50 voucher code to redeem the £100 discount promotion.
The customer service representatives were unhelpful, adhering solely to their scripted responses.
A Samsung code error prevents the promotion from being correctly applied. To utilize the £100 voucher, at the payment page (not checkout page), enter the APPS25 code first, followed by the £50 promotion code (if you have received it). This will result in the £100 promotion offer being applied.
Please note this only works with the Samsung shop app not the Samsung online store