My insurer usually sends out a form with the renewal documents for completion by the servicing garage every couple of years. I've now had my car 3 years and the agreed value has gone up £1,500 so well worth doing. In conjunction with the garage we looked at what similar model, age and mileage cars were available on Autotrader to help determine the value. No charge was made.
But that is what the insurance company will do in the event of a total loss, so why bother ? Standard insurance and no bother with NCB. Surely agreed value is for older cars where the the value is difficult to assess.