We don't use the same converter, but the first general rule would be that if what you're doing affects the highlights substantially, you want to do it in the RAW converter. That's where the converter is working with more data. WB & exposure for sure. Shadow detail can be controlled much better in Photoshop, so set a low or conservative black point with the converter. I'd make only a basic/minimal contrast correction, leaving room for more exact contrast tweaking in PS.
The second general rule would be to work in PS instead of the RAW converter on stuff that you aren't sure about, & want to be able to fine-tune - perhaps repeatedly - with an Adjustment Layer. Curves affecting shadows, & all color adjustments other than basic white balance, are better handled with Adjustment Layers. I've found it especially messy to boost saturation very much in RAW conversion - it's better to have access to the individual color sliders on a HS Adj Layer.
Re: what you mentioned about WB: Rather than go with As Shot for WB, I always take a look at Auto. My camera (5D) usually makes a pretty good guess about where to start from. And I also always try to correct for a neutral gray highlight with the eyedropper. Then tweak whichever looks best.
Kirk