I had two codes in my PS3 CE.

The first code was 4-4-4 code that is to be applied via Account Management>>Redeem Codes from the PS3 Home. That grants you your +30 days and the CE Items (which are delivered by Moogle Mail in game). I found that once I'd applied the code I then had to restart the FFXIV client, it asked me to reconfirm I was linking my SE account to this PSN account and then once I'd managed to log in all the items were waiting for me in my in game mail, which you can pick up from any of the Delivery Moogles, and my account had been credited with +30 days. You can check that via the Mogstation link from the Final Fantasy Lodestone home page.

The second code I got was a much bigger code and was directing me to a members site somewhere (the URL was printed on the text), however I have yet to find a way to use that code as the URL it directs me to is not accessible.