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I like to break down the mechanics of the pick's interaction with the string as 3 different periods, separated by 2 key events. The periods are approach, displacement, and resonance. The events between them are contact, and release. Chronologically, that's approach, contact, displacement, release, and resonance.
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=== Approach ===
The ''approach'' is not necessary. You may being your picking stroke with the pick already pressed against the string. I often do this to mute the string, then get a near perfectly "clean" sound to the note.
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=== Contact ===
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''Contact'' is when the pick first touches the string. If the approach was lengthy with a high velocity, there will be a slight audible thud on contact. It will be noisy rather than musical. This can be desirable or undesirable depending on context - it adds more noise and volume to the initial attack portion of the note, making it sound more raucous. On the other hand if the approach was basically non-existent, there will be no thud, and the note will sound cleaner.
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=== Displacement ===
Other factors that determine how much displacement is available are the shape of the pick, and the angles it is held incident to the guitar's face and the string. In relation to the guitar's face, it can "hook" the string, avoiding release. Or it can allow for less displacement. Similarly, angling the pick in either direction away from perpendicular to the string offers less and less ability to displace it, varying depending according to the pick shape.
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=== Release ===
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While the ''release'' is nothing too interesting - just the string finally freeing itself of the force of the pick and attempting to return to its at-rest state, the transition from displacement to release is more interesting. Depending on the amount of displacement as well as the angles, shape, and material of the pick, as the string slides down the edge (or face) of the pick, it will make noise. Most of the time this will sound scratchy, although some smoother materials may be quieter than others. This energy does transfer into the string, which will resonate on each side of the pick. Thus, pick location on the string matters to this sound, and it is why pick slides have their characteristic sound.
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=== Resonance ===
That said, you may not always want that. Different angles can give different pick attack noise signatures as well as affect the level of overtones vs. the fundamental frequency. A lot of this depends on the pick material and shape, and the exact nature of your picking motion. Its best to experiment with it. A completely perpendicular angle is going to be sharper on the string than otherwise, and with an approach that has significant velocity, this can also trigger harmonics in the string.
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== Location on the String ==
But don't rely on changing positions to dial in that tone. Move your right hand around to try some new tones out. For an extra smooth lead, make sure you are picking exactly in the center of the resonant portion of the string; move back towards the bridge for a more aggressive tone.
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== Dynamics and Fret Buzz ==
Picking even stronger, you can get even the sustain portion of the resonance to slap against the frets, getting a consistent buzz. This will overpower the actual note itself, and should be used sparingly.
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== Breaking down the Rules ==
Rather than picking directly through the string, you may want to pick diagonally through the string, to add some scratching to the pick attack.
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=== Pick Angle Incident to the Guitar Face ===
On the other hand, angling the pick the other way will make it difficult to impossible to apply tension to the string without pushing through it and getting an early, weak release. The sound of the pick sliding against the string may be as loud or louder than the sound of the ensuing resonant string. Again, this is bad practice for a novice trying to gain pick control, but another weapon in the arsenal of a master. It is like the reverse of an accent. Your audience can hear that you are trying to playing a note, but barely anything musical is voiced. It is like a dying man trying to utter his last words - the incident noise is there, but what is he trying to say? In the extreme it is painful to listen to (just like a ridiculously strong accent). But done tastefully, it can earn you legendary status.
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== Accents ==