NOTE: Your gameplay experience will be INFINITELY better if you use a flightstick (remember people who still use those things?) or a gamepad, especially a PS2-style gamepad. You will want to have your controls properly configured - take the time to do this or else you'll find yourself fighting with the controls instead of using them. You are a PC gamer, keyboard and mouse is great, but this game was based off a console game, and this game is not the only console-style game out there, please take the money to get a gamepad. It'll make your overall PC gaming experience even better.
I played the X-Wing Collector's CD-ROM on my Mac Performa 637CD over a decade and a half ago and I had a blast. I also enjoyed the immensely popular X-Wing vs TIE Fighter when it came out later and really enjoyed the space assault missions in Star Wars Battlefront 2. I saw this on sale during the "May the 4th be with you" sale for $1.69, and I have to say, for less than the cost of a drink, it's a really good deal. Once you get your controls in order, the game feels really good.
It's an arcade space flight sim, much along the vein of Rogue Squadron 64, so you don't have to worry about things like managing your front and aft deflector shields or figuring out how much power you want to get into your engines, etc. If you've played the space assault mode in SWBF2, this game plays exactly like that. I suggest mapping your your boost/brake not to your triggers, but to your right analog up/down - it makes flying around much easier to deal with.
The missions are extremely fast paced and most of them are pretty short. This game is great for quick "get in, get out" play sessions. Unlike X-Wing, where a lot of time is spent on the buildup towards the missions, this game gets you right into the thick of the action.
The story is so-so, three random people end up teaming up together by chance to take on the evil Trade Federation. You've heard it before and like any game, it adds to the universe that these games have built up. Granted, if you've heard the news, Disney-LucasArts have officially said that none of the games or books are canon, but I'd say considering the amount of milking they've done of the franchise, they're still good enough to stand as their own stories.
Word of warning, although the game runs fine on modern systems, the highest the game will run at (without registry edits) is at 1280 x 1024, and most of the textures are upscaled so they'll sometimes look blotchy. However, it's a 12 year old game, so that's to be expected. I've been told that the Steam version of this game was "GOG'ized" to make it run on modern hardware and to detect modern gamepads, so that's definitely a plus. For $5, it's a bit too much, but if you can get this during a Steam sale, definitely get it.