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Alignment and tire pressure could affect your MPG, but I don't think you'll get another 5MPG from that.
I've found that really having good control of your throttle helps quite a bit. Aggressive driving = poor gas mileage.
Increasing tire pressure lessens the contact patch, which in turn lowers rolling resistance, making your car roll easier. You can actually get tires that are made for less rolling resistance nowadays as well. A good alignment can help lower rolling resistance as well.
If anything, learn to use your cruise control. That will help a lot right there.
And keep your trunk and back seats clear of clutter. The less weight you keep in your car, the better.
