Answer to both questions and this relates to May 2022.
If I recall correctly shuttles were being called for from around 7.00 a.m. obviously depending on your flight time. As I said we had FBC.
Train Station shuttles: We had stayed for a week in Venice prior to catching the train from Venice to Ravenna. When we arrived at Ravenna X shuttle buses, which were complimentary, were there to meet passengers alighting the train and before leaving the staff checked the station to ensure they had not left anyone behind. As we did not require the reverse procedure I am unable to help you there - best ask X.