That guideline of capturing toward the center usually holds, though there exist a few general exceptions of which I'm aware:
(1) In double e-pawn openings (like the one you showed, especially in the Ruy Lopez, Petrov's Defense, and Four Knights Game), the d-file needs to be left open for either player recapturing at QB3, since that gives the queen mobility along that file, which is critical for regaining the e-pawn by tactical means in some variations. In such cases, Black would prefer to play ...dxc6 instead of ...bxc6. A look at a database for such positions will confirm this.
(2) Sometimes in double e-pawn openings (especially in the Four Knights Game), a player wants the b-file open for aiming a rook down that file, especially if all the other files are closed or half-closed. In such games White would prefer to play bxc3 instead of dxc3.
(3) Occasionally (though I can't think of any specific openings or examples offhand), immediately after castling kingside a player wants immediate use of his rook on the f-file for attacking or tactical purposes, whereupon White prefers fxg3 over hxg3.
How did I learn those important exceptions? Sadly, they're rarely mentioned in books, except as a side comment instead of a general principle to know, so I had to figure those out from such book asides and extensive database game perusal.
Hey, there are many times in opening positions where your opponent will take your knight with his bishop or knight etc, and when all is said and done you are left with the decision of taking with the pawn toward the center, or away. (e.g. Roy Lopez where the bishop takes the knight, or the position I have shown.) I've heard the general rule is take towards the center but we all know that this is not always best, as is the case with the positions I have mentioned. What are the strategies that go into this?