You certainly can develop for Stackless but there is currently no specialized support for Stackless. This means that you'll find the code editing experience and the REPL window work just fine. But profiling and debugging, which rely upon sys.settrace, won't work for tasklets.
If you install Stackless via the MSIs PTVS will pick up the installation as it would any normal CPython installation. If you've installed it via some other mechanism you'll need go to Tools->Options->Python Tools->Interpreter Options and setup a custom interpreter using the Add Interpreter button.
If you'd like to make this better you can contribute back to PTVS to improve this. Stackless's documentation has information on how to enable debugging and it doesn't look like it'd be too difficult. From the PTVS stand point this would just involve updating visualstudio_py_debugger.py to detect that it's running on Stackless and add the appropriate code and make sure it works.