Dave,
You can just connect the USB in to your RaspberyPi and that is all you need to have a isolated serial connection. On the SBMS0 WiFi/USB board there is a UART isolator the MAX14851 and after that there is a UART to USB converter.
ESP32 will be disabled as soon as you set the UART as active in the SBMS0 menu.
And yes if you power the board through USB the 3.3V will be already present there but if you connect the USB to Raspberry Pi then you already have both the power need (just a few mA) and the UART interface trough the build in UART to USB converter in the SBMS0.
The max reliable speed through USB is 460.8Kbps but even 115.2k is more than sufficient as there is not that much data.