The answer to this involves a little math, and a little physiology. It's a little beyond what's covered in an average EMT-B class. It's something that should be covered in medic school.
Oxygen is carried in the circulation in two forms (1) bound to hemoglobin, (2) dissolved in the plasma. We can actually calculate the amount of oxygen carried in arterial blood. This is called the arterial oxygen content or CaO2, and is defined as:
CaO2 = (1.34 * hgb * SaO2) + (0.003 * PaO2)
Where hgb is the hemoglobin concentration in g / dL (normal male about 14-18, female 12-16), SaO2 is the saturation percentage expressed as a decimal (i.e. 100% saturation = 1.00, 98% saturation = 0.98). The PaO2 is a measure of how much oxygen is dissolved in the plasma, as this is a dissolved gas, it's a partial pressure, measured in mmHg. [I've omitted some of the units from this equation, but the end value for CaO2 is expressed in ml 02 per dl arterial blood).
So for the hypothetical situation of an individual who has a 100% oxygen saturation, breathing room air, we can infer that their PaO2 is going to be around 100mmHg. We get this from the oxyhemoglobin dissociation curve, which you can see illustrated here:
http://en.wikipedia.org/wiki/Oxygen–haemoglobin_dissociation_curve or better yet, in a good physiology text. It can also be measured with an arterial blood gas.
If we assume this person is a male with a hemoglobin of 16 g/dl, we can fill in the other values, and calculate (1) the amount of oxygen carried on hemoglobin, (2) the amount of oxygen dissolved in the blood, (3) the total arterial oxygen content.
So, first, the hemoglobin bound hemoglobin
= 1.34 * hgb * SaO2 = 1.34 ml /g * 16 g/dl * 1.00 = 21.44 ml
Then the dissolved oxygen in the plasma
= 0.003 * 100 = 0.3 ml.
For a total oxygen content of 21.74 ml, of which 98.6% is hemoglobin bound, and 1.4% is dissolved in the plasma.
So, when we look at this, the first thing we get, is, hey, the vast, vast majority of oxygen is transported as hemoglobin.
Now, of course, our patient is breathing room air, this is diffusing across the alveoli to give us an arterial PaO2 of about 100 mmHg. If we assume we're at sea level, ambient air pressure is about 760 mmHg. 21% of the ambient air gives a partial pressure of about 160 mmHg. This is what we're breathing in This is getting reduced as air in the lungs gets humidified, there's a little bit of shunting -- for a whole lot of reasons this ends up as around 100 mmHg in the arterial blood.
If we give around 100% oxygen, we end up increasing the amount of oxygen in the ambient air from 100 to 760. And we'll end up raising the PaO2, the amount of oxygen dissolved in the plasma. We're not going to raise it anywhere near 760 mmHg, but it's going to increase.
But not by much.
For every 50 mmHg we are able to raise the PaO2, the oxygen content is only going to go up by 0.15 ml. This is an increase of 0.7%.
The point, that I'm finally getting to, is that once the hemoglobin is fully saturated, increasing supplemental oxygen is going to have minimal effects on total arterial oxygen content.
The situations where this may be more relevant, would include
(1) the presence of dysfunctional hemoglobin, e.g. CO-hemoglobin, methemoglobin, where the oxygen saturation is falsely raised.
(2) When the patient is severely anemic, e.g. hemorrhagic shock, when less hemoglobin is present. But even in this case, if the available hemoglobin is fully saturated, additional dissolved oxygen in the plasma is only going to have a small effect.
Please understand, I'm not trying to talk down to you, or be condescending. I will happily explain more, if I can. All the best.