You can't import and export at the same time, I've found that if you plug in during the day, Octopus will schedule a charging session if your exporting, and that will mean you excess solar goes into the car, rather than earning 15p per kWh.
I've also found that Octopus will schedule an early evening session when I exporting in the evening.
I now don't plug the car in until I go to bed, my Victron system is also programmed to charge the house battery at 4kW when there is an intelligent charging slot, it takes the current house load including the EV charger and adds 4kW to it, then sets that as the grid point. If Octopus schedule a charge for 22:30, I guarantee they stop it by 23:00, then my system exports like crazy to try and get the battery down to 15% SOC by 23:30
Depending on your charger, it may also try to steal your solar exports, I had to alter the settings on my Zappi to get it to do what I wanted.
I've also found that Octopus will schedule an early evening session when I exporting in the evening.
I now don't plug the car in until I go to bed, my Victron system is also programmed to charge the house battery at 4kW when there is an intelligent charging slot, it takes the current house load including the EV charger and adds 4kW to it, then sets that as the grid point. If Octopus schedule a charge for 22:30, I guarantee they stop it by 23:00, then my system exports like crazy to try and get the battery down to 15% SOC by 23:30

Depending on your charger, it may also try to steal your solar exports, I had to alter the settings on my Zappi to get it to do what I wanted.