If you have a sealed container full of air in a closed system, say deep in intergalactic space, it will eventually cool to the temperature of the cosmic background radiation, which is about 2.7 Kelvin. Whenever an air molecule strikes the container, it transfers a bit of heat energy to the container and moves a bit slower. Meanwhile the container will spontaneously radiate heat energy in all directions. Since the outside surface is necessarily larger than the inside, over time all the heat energy will radiate away. Cosmic background radiation keeps it from ever reaching absolute zero.
Here on Earth, what happens instead with the same container is that it only cools to room temperature. Heat energy radiating away from the container is exactly matched by heat energy striking it from the outside, whether by atmospheric air or from random infrared photons from other objects.
So the question is this: Is the cooling of individual molecules enough to account for the force on the spaghetti? I don’t think it is. In any case, both the spaghetti and your lips are likely to be hotter than room temperature.
I think it’s more simple than that. The idea that air pressure only acts perpendicularly to any given surface is a generalization that only holds with a still body of air. Molecules move randomly; air pressure is a function of them striking a surface and each other. The likelyhood of a given molecule striking a surface exactly perpendicularly is actually extremely small. What actually happens is that the average effect of all the molecules adds up to a net perpendicular force across the entire surface. If the surface is flexible, like a balloon, then it forces the surface into something spherelike.
But with the spaghetti, we have a pressure differential, and therefore movement as the air molecules try to fill the area of lower pressure. Forget about the spaghetti for a moment. Imagine a supply of compressed gas: a helium tank, a can of air for cleaning your keyboard, a propane tank, whatever. When you open the valve, the gas rushes out through the opening, however small. Near that opening, the net force on the inside surface is not perpendicular anymore. More molecules are moving towards the opening than away from it, and so the net force is in that direction.
If you just suck in some air through your mouth, the same thing happens. Now add the spaghetti, and the only difference is that it gets carried along for the ride. There isn’t a sharply delineated zone wherein all air molecules striking inside that zone push the spaghetti into your mouth, and all those striking outside hit perpendicularly. Rather, it’s a gradient. Right at the lip-noodle junction, the net force is pointed most sharply inward. As you go farther back along the noodle, the net force returns to perpendicular.