Everything which just calls in the platformio tool can be used everywhere. This includes all the compiling, uploading, library and board management. There are however specific extension in the VSCode plugin like the interface to the PIO Unified Debugger (Debugging — PlatformIO latest documentation) etc.
So you can still fully develop using PlatformIO, and even manually setup the debugging session (refer Debugging STM32 and ESP32 targets in an IDE). There is also a CLion plugin in development which can be tested out (Debug by CLion · Issue #2201 · platformio/platformio-core · GitHub).