Hand-edited automation envelopes are always the best place to start, but even that won't always solve the problem in extreme cases. For that, you have to go old-school and do it the way it was done before dedicated de-essers existed.
Here's how to do it. Clone the vocal track. Apply a sharp high-pass filter to the clone, rolling off around 4KHz. Next, put on a compressor and smash the sh*t out of it with a low threshold and very high ratio. The clone track should now sound absolutely awful, with ear-piercing sibilance.
Now route that track to the sidechain input of a compressor on the vocal bus. Start with a moderate ratio and gradually increase it until the essiness goes away.
It's also a good idea to isolate a particularly bad "S" and analyze its frequency content. If it looks like white noise, you're good to go and the above method is guaranteed to work. But there are two scenarios that can be especially problematic: when there's comb filtering and when there's a narrow spike in the frequency response. If you need help with that analysis, email or PM me.