The station where I vollie has set schedules for both the daytime paid crews and the nighttime vollie crews. This station has 5000 calls a year, and we are also a training center, so we always have students who are along to learn. We staff 2 crews and a paid supervisor 24x7. Day shift has a 5th person - during the week, it is the Executive Director, and part-timers fill in on the weekends. The 5th person responds with the supervisor when the 3rd BLS unit is needed. We have 5 total BLS rigs, and when we go to 4th or 5th call, we have volunteers who show up to get the trucks out (because we only do that once or twice a month).
Our regular night shift schedule is 6p-midnight and midnight-6a. Some nights have full crews that run every week, and some nights have open spots that get filled in by volunteers picking up an extra shift (Most of our volunteers run only one shift a week). The system works for us, and every primary EMT/Driver on the schedule gets some extra incentive points when the schedule is full and we don't need paid staff to fill-in. We've gotten 40 or 45 weeks with 100% coverage for the last couple of years.
Another local squad has a combination of people 24x7. Some full-time paid staff with regular shifts, some volunteers with regular shifts, and then whatever gaps in coverage that haven't been filled by volunteers are offered to the part-time paid staff the week or so before - this is a squad with a much lighter call volume, but they also have a lower number of active members.
Schedules make sure that people don't get burned out. At the busy place where I vollie, each crew gets at least one call each shift. Additionally, becauase of the location, I need to stay on-station when I run. If it was a smaller community, I might run 3 nights a week, but only get 2 calls.
Depending on the situation and the call volumes, you may need a detailed schedule, or you may need something more casual. There are electronic scheduing programs out there that allow you to check availibility and coordinate everyone's schedules. My squad uses a Excel spreadsheet that is posted in a password-protected portion of the squad's webpage, so that we can remotly check the schedule. The supervisor's edit the schedule on the network several times a day, and there are also copies posted at the station.
Now, if you have lots of members showing up on calls... maybe you just need better communications. How about a highband channel that everyone can talk on, and that way, you can hear as others respond. My local FD issued highband portables to many of the active senior firefighters so that they could status that they were responding to the station - that meant that the paid staff would wait on the ramp for them to pull up, rather than responding with a light crew.
I suggest highband because it ISN'T monitored by our county, that way we can use it as we see fit, and we don't have to tie up a dispatcher. The channel is monitored in the station, so we can all hear it when someone calls on it.