Yeah it's a very easy game to pick up and learn, and it's really, really good.
Both the Alien and Predator Legendary Encounters games were the first/only deck building games I've ever played and I love them both. They're a ton of fun, and playing the different movies (in either game) makes for great variety, though each one is also extremely replayable on its own. In the case of Alien the difficulty varies between movies as well, (Alien and Alien: Resurrection are really tough, whereas Aliens and Alien 3 are much easier) so if one keeps kicking your ass you can always just try another one instead (though it's also great to replay the tougher ones to try and beat them).
The theming is great too. They all follow the structure of their respective films, and each one has its own unique mechanics that fit with their respective films, so each one really feels like it fits what it's based on.
And I definitely wouldn't worry about not having many people to play it with. It's still great even if there's just the two of you, and it can be played solo too, so technically you don't even need anyone but yourself!
Like Hicks said it's a good idea to watch some Youtube videos to get an idea for the mechanics and the flow of the game etc., and if you like what you see then you'll definitely enjoy playing it yourself.