Honestly, between the fact that you're on TOU-C (small price differentials), don't have much usage in 4-9pm, and have a separate EV meter, it may not matter much financially which mode you choose. You should probably just try different settings and see how the system performs for a week or two at a time and see which one you like the best, based on your personal preferences.
The bigger question is whether there is an opportunity to save money by changing the rate plan and changing the Powerwall settings to optimize against that. It really depends on your net kWh over the year and your prior true-up dollar balance. If you're been negative dollars in prior years or are close to zero net kWh, then there may not be much or any opportunity for cost improvement.