The short answer
The sock is identical in both boxes, so this comes down to whether you want Owlet's camera. Either way you get the Dream Sock, a UKCA and CE marked medical device that reads pulse rate and blood oxygen from birth to 18 months and sends alerts to a base station and your phone. The Dream Duo adds the Dream Sight camera: 2K video with night vision, a 130-degree lens, two-way talk, cry, sound and motion alerts, and room temperature and humidity, all in one app.
The Duo is around £380 against around £280 for the sock alone, so you're paying roughly £100 extra, about what the camera costs on its own. There's no separate parent unit, so video lives on your phone, and both inherit the sock's quirks: careful fitting, a daily charge, and testers reporting false alarms and base station drop-outs.
My call: the Dream Sock on its own, especially if you already have a video monitor. Choose the Duo only if you'd buy a Wi-Fi camera anyway and want everything in one app. And remember that no monitor has been shown to prevent SIDS, so neither replaces safer sleep: baby on their back, in a clear, flat sleep space, in your room for the first six months.