One thing I found systemd really confusing was its treatment of ExecStop in a service script. ExecStart is the command to run when systemd starts the service at system boot up (or when a user tells systemd to start the service). However, ExecStop is run when the starting command has finished running. You have to set RemainAfterExit=yes to have the desired function of running the stop command on system shutdown or on user stopping the service. ExecStop is basically the "on-cleanup" event rather than "to-shutdown-the-service" event.