If you have two identical signals panned to the left and right, it works out to the same thing as having one signal panned in the middle - center panning is just having the same level on both speakers.
Now, as you say, adding different effects to each of them will start to thicken things up a bit. One thing to be aware of is that, depending on what effects you're using, you might find that the two signals start getting out of phase and cancelling each other out. If someone's listening on a bad stereo, or in a bad room, or in a mall that doesn't care about stereo, your guitars might disappear altogether.
It *can* be done, but it's rarely the best approach.
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