Benb320: I input my credit card details, but the green checkout button remains unselectable. I've tried Chrome, firefox and edge now, all with the same result.
Seeing that you are new you might make a mistake that has cought several newcomers here unaware:
You can not buy DLCs to games that you do not have on GOG. If for example you are trying to buy the DLC for The Witcher III without having the game on GOG that won't be possible without getting the game on your account first. If you bought the retail version of The Witcher III you should find a code somewhere in your box (usually on the back of the manual) which you can use to redeem the game to your account and only then can you continue to buy the DLCs.
If you aren't trying to buy a DLC simply disregard the above. But that is a possible reason why you are unable to buy something.