Fallout: New Vegas: Courier's Stash is a complete value call. The additional Stimpacks were a lifesaver considering where I was in my game (getting ready for the
Lonesome Road DLC), though I found no use for any of the other items. By now I have much better gear, so the additional "Starter Items" did nothing for me. Even if I was starting another character, I would personally want to skip out since I like the "desert scavenger" experience.
I do, however, recognize a few players will want an extra little boost from the start. If you're in that number and considering picking up Fallout: New Vegas (and, if you haven't played it, you really should), the Fallout: New Vegas: Courier's Stash is an okay pick-up for the price.