Hello @Damian Hall?
I'm sorry to hear that you have found that the UI for initiating a video chat to be confusing. However, I can assure you that once you begin experimenting with the video chat feature, you'll find that it is indeed very user-friendly.
You can begin a video chat in a number of ways, including with a colleague with whom you have not had a prior chat. To do so, you click the Video Chat icon on the Collaborate sidebar. You can then search for and invite any one of your colleagues to the video chat.
You'll find this, and the other methods of beginning a video chat, described in the Start a video chat article (https://help.mypurecloud.com/articles/start-video-chat/) in the Resource Center.