"Po" never occur at the beginning of a sentence. They usually come after a verb. Sometimes there is an enclitic pronoun after the verb and so "po" comes after that.
In standard, formal Tagalog the only enclitic pronoun that "po" would follow is just the first person pronoun ko. The 2nd person pronouns "mo" and "ka" do not co-occur with "po" and "ho."
Example:
Ginawa ko po ito.
“I did this, sir/ma’am.”
In informal, colloquial Tagalog "niya" and ‘nyo (the short form of ninyo) behave like enclitic pronouns and therefore they go before "po" and "ho."
Example:
Ginawa niya po ito. (As opposed to Standard Tagalog Ginawa po niya ito.)
“He/she did this.”
Enclitic particles then follow enclitic pronouns. Keep in mind that "po" is just one of several enclitic particles. When there are more than one enclitic particles in a sentence, they have to be ordered in a particular way according to their class, as defined by Paul Schachter & Fe T. Otanes in their 1972 work Tagalog Reference Grammar.
According to section 6 of Schachter and Otanes, there are four classes of enclitic particles:
Class 1: na and pa
Class 2: man
Class 3a: ba, din, kasi, ho, lamang, nga, po
Class 3b: daw, muna, naman
Class 4: kaya, pala, sana, tuloy, yata
This means that the following sentences are grammatical:
Wala pa po si Juan.
“Juan is still not around, sir/ma’am.”
Tumawag na po yata si Maria.
“I think Maria has already called, sir/ma’am.”
Whereas these ones are not:
*Wala po pa si Juan.
*Tumawag na yata si Maria po.
It does get a little more complex. Schachter and Otanes explain: “Those class 3 particles listed in subclass 3(a) never follow a class 4 particle; those listed in subclass 3(b) may follow a class 4 particle.”