You can skip this message if it is more confusing than helpful -- it's hard to describe without a picture.
The way to think of 16pi/3 is that we're thinking of going around the unit circle that SynthDude2001 mentioned. Every 2*pi is one complete revolution around the circle, and we end up back at the starting point. So sin(16pi/3) = sin(2pi + 2pi + 4pi/3) = sin(4pi/3).
To relate 4pi/3 to one of the previously mentioned angles of 0, 30, 45, 60 and 90 degrees, think of pi as half way around the circle or 180 degrees. 4pi/3 = pi + pi/3, which means we go half way around the circle, and then 60 degrees more. The 60 degrees tells us that the answer is going to be some variation of sqrt(3)/2, but is it negative or positive?
To answer the question of if it is positive or negative, we need to think of sine as "opposite over hypotenuse", but what triangle are we talking about? If we go back to the unit circle, the hypotenuse is the line going from (0, 0) out to the point on the circle. The "opposite" side is the line parallel to the y axis, and the "adjacent" side is the x axis. When we go around the circle by 4pi/3, we end up in the lower half of the unit circle, which means that the "opposite" line goes down into the negative side of the y axis. This means that sin(4pi/3) will have a negative value. If our point on the unit circle were on the positive side of the y axis, our value for sine woudl be positive.
Combining the two pieces of information (that sine(60) = sqrt(3)/2 AND that sin(4pi/3) must be negative), we can finally respond that the answer is -sqrt(3)/2.