I bet the problem is when you are trying to replace values with a new one, one that is not currently part of the existing factor's levels:
levels(iris$Species)
# [1] "setosa" "versicolor" "virginica"
Your example was bad, this works:
iris$Species[iris$Species == 'virginica'] <- 'setosa'
This is what more likely creates the problem you were seeing with your own data:
iris$Species[iris$Species == 'virginica'] <- 'new.species'
# Warning message:
# In `[<-.factor`(`*tmp*`, iris$Species == "virginica", value = c(1L, :
# invalid factor level, NAs generated
It will work if you first increase your factor levels:
levels(iris$Species) <- c(levels(iris$Species), "new.species")
iris$Species[iris$Species == 'virginica'] <- 'new.species'
If you want to replace "species A" with "species B" you'd be better off with
levels(iris$Species)[match("oldspecies",levels(iris$Species))] <- "newspecies"