Capture pollinators and wash their bodies in aniline blue drops placed on a glass slide and observe under microscope. Count the number of pollen grains present and accordingly evaluate their pollen carrying efficiency. Further, in case of honey bees, do not take pollen from their corbiculae (because there will be loads of pollen and hence avoid corbiculae). Count only pollen grains present on other body parts of these honey bees.
One method we have used in the past is to cut off inflorescences when the flowers are in bud and bring them back into the lab until they open and can be taken out for single visit experiments. You need to have a set of control inflorescences to make sure that moving them doesn't result in pollen deposition on stigmas of course.
By the way do you mean "effectiveness" or "efficiency"? They are not the same thing.
the another possible method is just collect the flowers immediately after the single visit of each/respective pollinator. Similarly collect flowers after pollination (before withering) and fixed them on cotton soaked in FPA solution. Dissect the stigma on a clean slide and count the number of total pollen grains (species under study). These exercises would give you an estimate of pollinator effectiveness and pollination efficiency.
If you want to determine the efficiency of a pollinator by looking at pollen deposition on the stigma, you still have to protect your flowers from pollination before you start your observations. You could shield the whole plant by putting a cage over it, in case you are talking about a small herbaceous plant. For a shrub or tree, you could use a cage around a branch, which is not hanging, but supported from the ground.
We've tried just about everything in order to pollinate mango flowers without contamination. The only way we achieved limited succes was by caging the inflorescence and maintaining the pollinator (in this case common houseflies) enclosed and in constant contact with the panicle for a minimum period of ten days..
However it is very difficult to assure complete success as we had problems with non flying invaders such as ants and thrips.
In the case of hand pollination in vitro we managed significantly successful pollination as follows:
1. Cut panicles at anthesis of majority of flowers (>80%) within the lower1/3 of the panicle.
2. Bag panicles in a thermos at 13°C , rush to the Lab. and place in a nutrient solution or distilled H2O
3. Emasculate receptor flowers and keep in an adequate agar preparation
4. Exrtract pollen from donnor stamens
5. Apply pollen to receptor flowers
Nevertheless I feel that it is almost impossible to acquire uncontaminated receptor flowers wihout some sort of bagging.
HINT. In mango timing is of the essence as hermaphroditic flowers are only receptive at precise temperature and RH which in our case (Southern Mexico) occurs from 8 to 10 A.M.
I dont know what species you are working with or under what ecoclimactic conditions but may I suggest you try working along this line. You might get away with collecting clean uncontaminated flowers before undesired pollinators beat you to them.