To answer your question about pressure cooker vs pan cooking, the answer is...it depends.
You're right about the pressure cooker speeding things up. And if your recipe is pretty basic, you probably won't notice much of a difference in flavor between your pressure cooker method and a slow pan cooking.
But if there are a lot of spices and time for flavors to meld, maybe even different spices added over the cooking time, then the slow pan method is going to make a difference. While the pressure cooker will make things cook faster, it won't necessarily make the flavors extract dramatically quicker, so you may find that the flavor hasn't really peaked in the shorter cooking time. Or if you expect wine, for instance, to permeate into the meat, it will do more of that over a longer cooking time, than the short, but more intense time that your food spends in a pressure cooker.
An easy way to decide might be to think about if you have one of those recipes that is "better the next day". That recipe is likely to benefit from the low slow pan cooking.
In the end, your best bet is to make it twice, in a reasonably short space of time, and then decide for yourself.
But there are some days when you just need to get the food on the table, and as you've experienced, the pressure cooker is one of the greatest kitchen time savers I know.
I can't speak to specific chemicals/aromatics for mushrooms, but this kind of thing does happen with all kinds of food. The initial cooking is releasing aromatics that were previously bound up in the food somehow, so you quickly get some stronger flavors. But aromatic molecules are volatile (that's why you smell them!) and also generally more prone to breaking down, so as you cook longer, they escape, or are broken down into something else without so much flavor, leaving you with something milder.
Think about onion, for example. When you first start sauteeing it, there's a lot of really strong onion smell coming off, maybe even enough to make you cry if you're prone to it. If you eat it then, it'll still have plenty of sharp onion flavor. But as you cook longer, those flavors mellow out; going to the extreme, slowly caramelized onions have no sharpness and very little onion flavor.
I think the initial strengthening of flavor may be stronger with mushrooms because of their structure. They seem dry at first, with all the water bound up inside. But as you start to cook them, their structure breaks down and they quickly release a lot of water, and with it, those flavors.
Best Answer
What gives spices their flavors are the oils that they contain, along with any water soluble flavors that they might have. In a pressure cooker, your food will cook hot. What that means to your spices will vary as certain spices could grow more bitter or sweeter depending on the compounds inside them. Conventional wisdom says that pressure cooking concentrates the flavors, although that would seem to fly in the face of physics as you aren't reducing while pressure cooking, you are just heating steam at a higher atmosphere to transfer more heat to the food faster.
As for texture, use the one that you like.