Verizon uses CDMA and T-Mobile is GSM. The two are not compatible.
There are phones that have both types of radios but I'm not sure if the S4 is one of them. It may also depend on which particular model S4 it is.
At the very least the phone would have to be unlocked by the old carrier to move over but even then it might not work. Even if it does have the right type of radio it has to be activated and be on the right bands.
I suggest you ask over in the S4 forums, you should get an answer there.
You will only get 4g(HSPA+) if you are in one of the refarmed areas. Verizon is weird. Pretty much all of their 4g LTE phones come unlocked now a days. It all depends on the bands the particular model supports. Older phones(s3 etc) need to be on kitkat. You may encounter other problems.
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