We did it about 4 years ago. The following info about PS for the chef's table was current then, but you should double check to see if anything's changed. As I recall, they only had one seating a night, and it was only available 5 of the 7 nights. There was a much longer window on when you could call than for usual PS -- 180 days I believe. We wanted it for a particular night, and so I called exactly 180 days before, at about 2 mintues after 7:00 in the morning. No dice -- too late, someone else had gotten it just before us. So, I called the next day right at 7:00 and got it for 180 days later. I seem to remember there was a separate number to call for the reservation.
It really is an excellent experience. Once you decide to do it, don't read too much more about it, as there may be a few surprises you might not want to know about in advance. It's an eye-opener in terms of how a major resort kitchen operates. We got in just as the prep work was being completed, and were there through the first seating and up to about the entrees on the second seating. So we got to see just about everything -- the frustrated waiters, the returned meals, the crush on the grill guy of 18 items on the grill at once, the letdown right after the initial desert crush before the second appetizers etc.
Whether or not you will find it romantic depends on your view of romance. It is very interactive, and there's sort of someone around all the time, although the table is set off just a little so you can have privacy if you talk quietly. There are many reminders that you are in the middle of a working kitchen -- for example, they had foie gras the night we were there, so there was a 5 gallon clear bucket with goose livers soaking in milk in front of us. I can understand why some might not find that romantic; it was right up our alley, though.
As for the food, if you're a hard-core restuarant connoisseur, you might be somewhat disappointed. Most every dish is excellent, but there's really no overall coherence to the entire meal. It's most a big food orgy, not necessarily a balanced menu of integrated courses. (Although you do have the opportunity to meet with the chef beforehand, and you could construct it a little differently from how they suggest it if coherence was your goal.) If you like to try lots of different things, and don't really care whether the chipotle-lime-cilantro duck goes with the later course of burgundy mushroom venison (just making that up, I don't remember what our actual courses were), then it's a great place. It was not cheap -- in fact, it darn near broke the bank. HTH