We were not on a Rick Steve's tour; we were hiking with REI Adventures. Our tour ended in Ljubljana so we actually boarded the train there, not in Bled. But before joining the tour we spent several days at Bled, arriving there by train from Munich. The Bled rail station (Lesce-Bled) is several kilometers distant from the lake. There was a shuttle waiting to take people into town, dropping at various hotels. I think we paid €5 each. You might be able to find out where this shuttle picks people up for the ride to the station.
After three days at Bled, we had to return to the rail station from the town to get to Ljubljana for our tour. Buses were on strike that day, so we planned to take a taxi, which would have been around €12. But the woman at the bus station kindly found us a ride with a shuttle driver who was heading to the station to pick up arriving passengers. He would not let us pay him.
Boarding the train at Bled rather than Ljubljana shortens the journey to Vienna by 45 -50 minutes. But depending how much time the tour gives you in Ljubljana, you might want to return there to finish exploring before heading to Vienna. We absolutely loved Ljubljana. In normal circumstances (I.e., no strike) you can take the bus right from Bled (by the lake) to Ljubljana.