The website you linked lists the various modules you can attach - I assume that the base PicoMate is simply a breakout board that sends GPIOs to various Grove connectors.
You can look up each of the devices on the ESPHome website to see if they are supported:
12 detachable and easy-to-use modules:
Push Button
WS2812 RGB LED
Rotary Encoder
Buzzer
Digital Microphone (ZTS6531S)
Digital PIR Sensor (AS312)
6-Axis IMU Sensor (LSM6DS3TR-C)
Digital Optical Sensor (LTR-381RGB-01)
3-Axis Magnetometer (MMC5603NJ)
Temperature & Humidity Sensor (SHT30-DIS)
0.96” 128x64 OLED Display (SSD1315)
Not all of the devices are supported in ESPHome (the LTR-381RGB-01 for instance or the LSM6DS3TR-C) but others are or may work with some tweak.
I suggest you share your yaml for the WS2812 RGB LED and we can have a look.