You do biometrics after you have submitted your application, and it's still done at a Post Office (costs £19.20).
As I understand it, when you submit your online application, your biometrics invitation letter will be generated. You print it, take it to a Post Office and get your biometrics done within the timeline it tells you on the letter (I think it's either 10 or 15 working days).
You also submit your application and documents to Sheffield within the timeline they give you (again, I think it's 10 or 15 working days)... though I believe this is done separately to the biometrics (i.e. you can mail everything before you have given your biometrics, as the biometrics are transmitted to Sheffield electronically).