With Canon cameras, even the latest sensors, you should always increase the ISO, without using the expanded values, so that you do not underexpose in the camera with your chosen shutter speed and aperture combination. Pushing the exposure by one stop in post is generally always worse than increasing the cameras analogue gain by one stop. In the older bodies I have I would actually say that using ISO 3200 correctly exposed produces better results than ISO 100 pushed one stop in post. I actually go further than that in that I Expose To The Right. When using ETTR you attempt to maximise the exposure for any ISO value so that you expose for the brightest highlight that you want to keep. You then bring the exposure down in post. This will minimise the noise in the image, without the need for any noise control. Of course although you have the best possible starting point for noise when using ETTR you may still need to use some NR.
Dan's explanation of Lr Export Sharpening is spot on. one thing that you should be aware of is that when using the Print sharpening options you should set the DPI/PPI value in the export dialogue to match the intended output resolution of the printer, as well as the paper type and strength. The algorithm that calculates the exact amount of sharpening to apply takes the DPI/PPI setting into account for printing. So although it normally doesn't matter what value you use once the file has been created, Lr does use it.
This only affects the level of sharpening for Print, if you select Screen the DPI/PPI value makes no difference, you just have to set some value. Personally I usually set it to 100, since it is close to the PPI value for the average monitor. Also if I see a JPEG floating around on my system I will know that it was sharpened for screen with that value. The lowest PPI that I can think of that would be passed to a printing device is 150 PPI for canvas prints.
Alan