Coming from Python web background. Trying both boards for prototyping.
Pi Pico W: simpler MicroPython port, less arbitrary 'why doesn't this work' moments. Slower (133MHz dual M0+). WiFi works but limited (no BLE).
ESP32: richer MicroPython (BLE, ESP-NOW, deep sleep extras), but more ways to mess up GPIO assignments. Faster (240MHz dual Xtensa). Native dual WiFi+BT.
For learn-Python-on-hardware path: Pico. Once comfy, switch to ESP32 if need wireless richness.
MicroPython hardware vets: agree or push back?