With barbell benches I find that my shoulders are overly involved. I can't get around it. I guess it's just the way I'm built. The only thing I get out of barbell benches is that I get better at doing barbell bench press. And I'm in it for the looks (from girls) and health benefits, not to see my bench press numbers go up.
Before I go into this, let it be known that different things work for different people. As I said above, I get nothing out of barbell bench presses, but depending on your build, you may find barbell bench presses the best exercise for developing chest muscles. Anyway...
My chest started looking better after I started working chest with back. This is generally what my routine has looked like for a while, after warm ups and stretching... (Where you see A.) and B.), and so on, denotes that it's part of a superset).
A.) Pull-ups (I usually add 5lbs by belt)..... 3 x max
B.) Weighted Chest Dips..... 3 x 8-10
Underhanded Barbell Rows..... 4 x 10-12, 8-10, 6-8, 4-6
C.) Incline DB Flyes..... 3 x 8-10
D.) Incline DB Presses..... 3 x 10, 8, 6
T-Bar Rows..... 3 x 10, 8, 6
(Lower Back Exercise, such as Good Mornings or Hyperextensions.... Usually 3 sets, 10-15ish reps)
DB Pullovers..... 3 x 15-20
I change it up some, but more or less it's about like that. The gym I've been working in kind of sucks, so I'm fairly limited in what I can do at the moment. But this works pretty well. I may remove (Lower Back Exercise) and replace with deadlifts once my conditioning gets back up (I'm coming back from an extended break).
Technique > How much weight you're using