throttle position sensor allingment

Yes you can do it with a multimeter, problem is that you need to know the values for you particular vehicle.
You can take the reading at rest with no tension on the pedal which will give you a resistance at idle.
Obviously you can take a reading at full throttle and at points in between but unless you have the specs for the TPS for your vehicle then you don't know what they should be.
Also check that nothing is interfering with the actual pedal travel, amazing what a bit of grit, sticks and small pebbles can do.
Most fuel injection systems these days self calibrate to a certain extent.
Probably the best thing to do would be to disconnect the battery for a few minutes to reset everything and then connect it back up, see if this solves the problem?

Most modern ECUs automatically calibrate for different TPS resting values. Ie they take the first idle example and use this from then on.

Really the only thing you should be testing if you have a hesitation problem is that he transition from idle to WOT is smooth with no drop outs with a (now rare) analogue multimeter.
You have not stated why you want to "calibrate" it , but symptoms of a faulty TPS are usually hesitation/ drop out when transitioning from override to accelerate. this is because the greatest wear area on the resistor is just off idle, ie where it spends most time.
Regards Philip A