A knowledge base article about My Duo app doesn't have an option to add accounts as detailed in the instructions. provided by the UC Berkeley IT Service Hub - Knowledge Portal
If your app does not have an option to add accounts, you may have downloaded the wrong application. Google has a similarly named "Duo" app used for video calls. The application required for campus authentication is Duo Mobile, which features a green, square icon and is developed by Duo Security, Inc.
For reference, ensure you have installed the app shown below: