The Can you hide your face from a facehugger? question made me think of a similar question: can facehuggers be tricked? How do they recognize faces? (They clearly recognize faces for a variety of animals.) There are plenty of androids in the Alien universe; have there ever been any cases where a facehugger encountered an android?
The attacked-to-face instinct is something that is part of the species reproduction system.
Observe a cat giving birth: it will know by default all necessary elements - the actual birth, the severing of the ombilical cord, the sanitization of the new-born, checking of life signs and later on the feeding process. A cat and all other species except now-days humans are self-sufficient when giving birth, because it's part of their species reproduction.
The process by which the facehugger attaches to a face is part of its genetic programming and he will be able to do it (he will know what to do by genetic memory). Some relevant conclusions can be seen from the first Alien movie, specifically how the facehugger deals with a human inside a space suit.
The facehugger still attacks the suited man, even if his face is not directly accessible. So the facehugger knows about its target, even if it is protected. Although the basis of its detection capabilities are not well known, it is still able to correctly determine if the target is a valid host. So it acts by adapting to remove the obstacle by secreting acid until it reaches the host. So this answered part of your question: it cannot be tricked, not in an easy way.
Note that it is less relevant if the Alien species was genetically adapted to breed with mostly human hosts or not, because they proved to be extremely adaptable and able to genetically improve themselves in a single generation.
As for synths, since Aliens could distinguish living organisms from non-living ones (like synts), there is no chance a facehugger would attack a synth for reproduction / hosting purposes.
I seem to remember from one of the Dark Horse Alien comics that facehuggers attack based on body heat, which is why they don't detect androids as prey. I can't remember if it's stated how they locate the face, but perhaps it's something like terrestrial parasites being drawn to the heat and moisture of breath?