Just to make a few things clear for everyone (and if anybody does see some problems jump on them please, because it's been a little while).
As alchemy has mentioned, simple diffusion will involve small molecules or lipid soluble molecules. It's really important that you all understand this, but also understand why this is occurring. The plasma membrane is made of a phospholipid. Yes, this is an amphipathic molecule, but it probably is important to note that the major component is that lipid. The polar region is certainly much smaller. So, lipids can pass through by simple diffusion as well because it only needs to get past a pretty week polar barrier to make it into that nice, lipid environment.
Small molecules can get through because they're just that, they're small. The phospholipid bilayer can't pack in perfectly, and by virtue of the fact that the cell is at 37°C and not -273°C, the phospholipids will constantly move and jiggle around. For small molecules, they can just weave through, even if they are slightly charged. The effect of polarity isn't enough to knock them away either.
So the key points there:
-the effect of the phosphate heads' polarity will not be sufficient to deflect a lipid molecule; a phospholipid is a mainly non-polar molecule. The lipid will just barge through that tiny deflection.
-small molecules can get through for two reasons: there are tiny gaps because the packaging of phospholipids next to each other isn't perfect, and because the effect of polarity, likewise, isn't strong enough to knock them back.
Compare this last point with charged molecules. Whilst small, they bare a full charge, which would respond too much to the charge difference between itself and the phospholipid. The charge difference between an ion and a polar molecule is greater than the charge difference between two polar molecules. In this case, the difference will be great enough to keep the ions out.
The membrane is one of the most incredible things in Biology. Its design is absolutely perfect and its chemistry astounding. These systems that you're learning about, various types of transport across the membrane, reflect the complexity of its chemistry. That's why there's so much to learn, because you really are learning about an incredible structure.