I'm afraid I can't help you with your formic acid problem (actually, I hope someone will give you the answer as I've pondered the same question on similar separations on occasion), but on TLC you cannot ever have two solvent fronts, except maybe when your solvents don't mix, and then you're doing it wrong anyway. However, sometimes an impression of two solvent fronts can arise, especially when the solvent starts to evaporate. Whatever happens, you always take the highest position of the solvent as your front to calculate Rf values with.