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As with everything else, genetics play a major role. Muscle insertion points could play a role but I suspect that if you were to lean out a little more, you'd have that "popped out" bicep appearence as you put it.
With regards to a "magical exercise" so to speak, you're best bet is to target the biceps from a variety of angles using a variety of equipment.
For example, perform barbell curls using a wider than shoulder width grip and you'll be placing more emphasis on the inside of the biceps. Utilize a narrow grip and you'll be placing more emphasis on the outer portion of the biceps.
Taking it even further, let's look at 3 different bicep exercises.
(this is all covered in our bicep training article by the way)
http://www.thefitnessblueprint.com/main ... age=biceps The biceps are maximally stressed during the first stage of flexion while performing preacher curls, the midrange of flexion while performing standing barbell curls and the last range of flexion while performing concentration curls.
Bill is dead on here, your genetics will be the determining factor whether you have that popping effect, and leaning out will help with apperance.
There are things like doing preachur curls on a vertical surface that really help.
Remember when you can do bent-over rows with 275+, dips with 100lbs strapped to your waist and chins with 100 stapped to your waist your arms will be as big as they will likely ever get!