Easy answer - doubled-float margin bug in IE.
This bug occurs when you have an element floated and then apply a margin in the same direction as the float.
In your case, you have #mainNav floated left then you apply a 10px left margin to it. IE DOUBLES that margin to 20px ! Same happens if you float right.
The fix ? Add height: 1% to the #mainNav rules. However, you should put that in in a 'iefixes.css' file (or whatever you want to name it) and add in the necessary conditional comment to make IE obey this additional rule. That leaves your main cSS file free of hacks that other browsers don't need. 
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