I would concur that Goldeneye has the benefit of popping a lot of people's multiplayer FPS cherry.
I had some limited multiplayer FPS experience, but that was always netplay. Goldeneye was the first FPS I had ever played that allowed four of us to sit around the same TV and just go nuts. Of course, there were other factors, too, which made it a unique experience. It was the first FPS I had ever had the ran well on a console. It was the first FPS I played (with the possible exception of ROtT) that wasn't sci-fi, fantasy, or that took place in the past. Even though the hits resulted in little more than a red blotch, it was also the first FPS I played that really allowed you to do more than just shoot someone in the chest. Of course, I can't leave out one of the best parts: one-hit kills. I suppose I am in the minority, but I love the action and fast-pace that it presses. Things really felt more frantic when you were always one shot away from killing, or being killed. It also opened up the door for knife kills, and slap kills. Nothing would be more nuts than maniacally slapping away at someone with an automatic weapon, and actually getting the upper hand.
Goldeneye also holds a special place in my heart simply because of when it came out. It was released during my senior year in high-school. This was probably the last time where I could sit around with friends, hours at a time, without a care in the world, and just dick around with video games. We wasted so many hours playing 007, listening to music, and beating the **** out each other for all of the dick moves we would pull (like proximity mines in the start points). When Perfect Dark came out, we were already losing our vitality. I was starting my junior year in college, worrying about buying books, worrying about work, and all of the other burdens that come with responsibility. Sure, everything just worked better in the game, and there were a ton more options, but it wasn't as fresh, and we weren't as carefree.
Every once in a while, like othes here, we would bust out Goldeneye. It is a shock to see just how dated it has become. But, just because of dumb nostalgia, it will always be untoppable as far as the pure fun it exuded.