Also, as you have suggested, she may mate whether she wants to or not. The 30 zillion studies alluded to in Anne Houde's book suggest that females do have a fair amount of choice in several situations in the wild. However in an aquarium, the female's choices of males are limited and she can't swim across the pond and hide in some weeds if she doesn't want the attention of some male. (The small town syndrome.)
Many species of livebearer, egg broadcasters and even some cichlids have smaller males who by all rights shouldn't get the opportunity to spawn because of the presence of larger males. However, these little guys are called "sneaker males" and do just that! Also, with a minimun investment in protein, the little guys are available for stud service if the bigger, more showy and therefore vulnerable to predation, males get taken out.
Multiple matings have a utility in nature in that it expands the gene pool. There is a controversial school of thought though that genetic diversity a some cases may be over rated. There are lots of cases where shrinking populations of animals have been found to be in big trouble as they reach a genetic road block.
A couple of sources have suggested post birth female guppies emit a pheromone to attract males. For an animal as far down the food chain as guppies, the imperative to keep producing as many young as possible must be great.
Saw the title of a study reported on at some academic conference suggesting multiple matings are also good for the female guppy. Don't have a copy of it, therefore will draw my own conclusions.
And one can never tell when a guppy is smiling. ;)
All the best,
u.s.