In short the answer is, NO. Up until 1999 or 2000, the all star game had less players and 90% of players picked at that time were worthy of the selection and recognition. Now, every team has to be represented, fans can vote for a player up to 25 times online with one email address for a player. It seems that half the rosters are of players we just don't know about. However, most importantly the games are mostly boring. The 2002 game was the last memorable all star game, because the game ended in a tie, and there were some fantastic plays made in that game (Torii Hunter's catch on Barry Bonds).
|2002 autographed all star ball. Jimmy Rollins and Shea Hillenbrand are noted here.|
So if you're going to collect player autographs based on all star appearances, seek out the players from pre-2001. Pedro Martinez's performance in 1999 is an example of an all star ball worth having signed. Or, collect autographs from all the all star game MVP's, including today's players. Another idea is to collect autographs on an all star ball from the players of your favorite team.
|Fred Lynn autographed 1983 all star ball. Fred hit a grand slam in this game to earn him the MVP.|
The reality is that an all star game appearance does not make the autograph more valuable. An end of season award (MVP, Batting average champ, gold glove) is what makes an autograph more valuable. I guarantee that by the next morning following the game you won't even remember who won the all star game MVP (JD Drew 2008).