I don't like going for the same players every time I start. I know who's available, and I search about for a while.
This time around I've got Magallanes, Joaquín, Sand (scores a ton off of his head), and numerous others. A lot of them have been mentioned already.
Into my second season, and I've already got a team that's been actually bought as opposed to acquired on frees.
GK - Rustu
DC - Chivu
DC - Hyypia
DC - Campbell
DM C - Vogel
DM C - Guardiola/Sergio
ML - Kily Gonzalez
MR - Joaquín
AM C - Aimar
FC - Ronaldinho
SC - Owen
I started as Liverpool (don't ask me why), which allowed me to get Michael Owen, Steven Gerrard (who I sold), Hyypia, Henchoz, etc. I bought Sergio as I was impressed with him in the CL over the past few seasons, and so I made him ever-so-slightly better in the game to reflect it.