Others mentioned the angle excess formula, so I won't repeat that.
Lets say the sphere is large and you can only access a small part of the sphere. Let's also assume that you have no direct method to measure area. (Can anyone suggest an accurate method to measure area without already knowing R?).
Lets say you can measure lengths and angles. Both these things can be done with fairly pedestrian tools. Let's also assume you can measure them with perfect accuracy. Otherwise any error you make will make it impossible to tell your triangle from a Euclidean triangle (we are assuming we can only access a small part of the sphere).
Well, under these conditions, you can use Spherical Trigonometry. If you have a compass you can make an equilateral triangle (using the same method in Euclid's first proposition). Let s be the measured side length and alpha the measured angle. (The angles are equal by the law of sines). Let x be the cosine of alpha (x is known by calculation!).
Let S = s/R. To determine R, we must determine S. By the second Law of Cosines:
[itex]x= -x^2+(1-x^2)\cos(S)[/itex]
Hence we can calculate
[itex]\cos(S) = \frac{x+x^2}{1-x^2}=\frac{x}{1-x}[/itex]
Taking the inverse cosine we can reconstruct R.
I will point out that in the euclidean case, alpha=pi/3 which impliles that x = 1/2. The formula would then give cos(S) =1, which means R=infinity, which confirms the flatness of the space. (I am only mentioning this as a check on my calculation)
Challenge: If we allow the measurements to have error, is it possible to adjust this calculation so that it can actually distinguish positive curvature from zero curvature? I suspect the answer is no since I have assumed that measurements can only be taken locally and a sphere locally looks like Euclidean space.