I did the My Way Spain tour last summer. In general you can look at the itinerary and on the days that you wake up in the city that you are visiting that day, you can book tickets for anytime after 9 or 10 am. The way the My Way tours work is that the guide is available at breakfast for questions, but if you have done your research and already know what you want to do for the day, you don't need to meet with the guide. You are free to have breakfast in the hotel and then walk or take public transportation to the different sites. So for example, on Day 1 of the tour, before the tour group met at about 5 pm, I had a ticket for the Sagrada Familia and then went to the Block of Discord and then went back to the hotel for the group meeting. On Day 2, I woke up and headed for La Pedrera and Parc Guell. I had advance tickets, but don't know if they were really necessary. In the afternoon I went to the Picasso Museum and Beach, and ended my day at the Catalan Museum. I had advance tickets to the Picasso and would recommend getting an advance ticket.
The next day we took the train to Madrid and were there by mid-afternoon so I had advance purchased a ticket to the Royal Palace which was open until 7 pm. I booked my ticket for late afternoon to account for delays in getting to Madrid, but since we were taking an early train to Madrid, I was fairly certain we would be there by mid afternoon. The next day, I woke up, had breakfast in the hotel and went directly to the Prado and Thyseen Museums. I spent the afternoon in Retiro Park. The next day, I went early to the Reina Sofia with an advance ticket and did the Rick Steves walk. I had spent time in Madrid previously and had gone to Toledo, Avila and Segovia, so spent my afternoon exploring a quiet neighborhood near the river in Madrid that the guide recommended.
The next day we went to Granada and didn't get in until late afternoon so I spent the evening exploring Granada. The next day I had advance tickets to the Alhambra and got up early and went directly to th Alhambra. I spent the rest of the day exploring Granada. I didn't need advance tickets to see anything else.
The next day we went to Ronda and there was nothing in Ronda that require advance tickets.
The next day we drove to Seville and I had tickets for late afternoon, 4 pm, at the Seville Cathedral. We arrived in Seville shortly after lunch so I had time to explore Seville before heading to the Cathedral. The following day, I went to the Royal Alcazar with a timed entry, advance ticket for as soon as they opened. I also had an advance ticket to the Royal Apartments. Those tickets are very limited in number, so if you want to see the Apartments, be sure to get an advance ticket.
So in short, on the arrival days in cities (Madrid, Granada, Ronda, Seville), you can plan on being there by mid to late afternoon and book tickets for late afternoon for the sights that are open late. On the days you wake up in the city, the day is yours to plan. For the must see sights, plan on seeing them on your full day in that city rather on the arrival day, and on the arrival day book tickets for sights you might not see if you get in late. However, as you might know already, the Rick Steves tour guides are very good about keeping the group on schedule so I didn't miss anything because we arrived to late in a city.
There were three group activities that you might want to plan around. One was a group dinner across from the Alhambra on the full day in Granada. The dinner was at about 5 or 6 so you might want to plan around that. The dinner was optional, but highly recommended. The second was a happy hour at a beautiful house in Ronda, again optional. The third was a flamenco demonstration before dinner on the full day in Seville, again optional. Each guide does something different and will let you know what the plans are on the first day of the Tour.