I haven't ever tried the S&W 22A, but I do own a Neos.
When I was looking to buy a .22 pistol, I tried handling several different models at the store. Out of all the .22 handguns the store had, I handled Ruger MkII's and III's, several variations of the Buckmark, a SIG Mosquito, an old Nomad, and an old French MAB .22 pistol. Finally, I came to the Neos. For me, I found that the grip was a perfect fit for my hands. I also found that it balanced rather well in my hands. And the final selling point for me was the ambidextrous safety, since I'm left handed. Once I actually got to using it, it grew even more on me. She'll eat any ammo I throw in her without jamming, and disassembly is very simple to do.
Now for the drawbacks. The trigger is rather crappy on them. Also, a lot of people don't like the sights on them. However, the full length rail along the top allows for mounting a red dot or other optics on it, if you don't like the sights.
Anyways, that's my opinions and experience with the Neos.