Published modules often provide the same amount of XP for achieving a diplomatic end to an encounter as the characters would have received for defeating the same encounter in combat.
I spend a lot of time creating NPCs (background, motivation, tactics, and statblocks) when making my own, and also a good amount of time modifying NPCs in published modules when I deem it necessary.
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Ignore XP altogether. Just run for 3-4 sessions and then at the end of the session say "Level up for next session folks."
Simple.
^ This. Things suddenly became much more interesting when we dumped XP altogether, since we notably didn't need to worry about XP anymore and instead wanted to know what happened next in the story.
It's easy to see why one could see experience points as only being rewarded for killing monsters, but in the Pathfinder Rulebook pg. 397-399 states several times that that is not the case.
"Designing Encounters: ... An encounter is any event that puts a specific problem before the PCs that they must solve. Most encounters present combat with monsters or histile NPCs, but there are many other types-a trapped corridor, a political interaction with a suspicious king, ..."
Assigning XP for roleplay really wouldn't be different from creating a combat encounter with the same XP. In your examples if you wanted to give XP for discovering new lands you would determine the difficulty of the task (Table 12-1) if average party level is 2 and you wanted for it to be hard the challenge rating would be 4. Table 12-2 says that CR 4 encounters give 1,200 XP (total).
Ignore XP altogether. Just run for 3-4 sessions and then at the end of the session say "Level up for next session folks."
Simple.
I'll heartily recommend this as well. Plus, you're stepping in as GM, the players shouldn't be expecting you to be instant expert with it, or super-accountant like an experienced GM ends up being. I'd focus (as GM) more on making an interesting story/experience rather than getting the mechanics down exactly. Juggle too many balls (encounters, npcs, magic, experience, storylines) and you start fumbling.
Oh, don't go all monty haul on magic items. its tempting, like the new babysitter thinking they can bribe the kids with candy and movies and fun, and still having problems getting them into bed.
Ignore XP altogether. Just run for 3-4 sessions and then at the end of the session say "Level up for next session folks."
Simple.
this.
Life is easier and takes less math. AND you guarantee that folks are the level you want them to be when you want them there.
If the PCs don't fight, make opportunities for XP based on righting wrongs, helping people, and improving situations.
Ie, Well/water-pump for the village is not working -- the PCs fix it? -> XP
One of the guys who knows all about the conspiracy was framed or is presently jailed for an unrelated offense. PCs have to exhorate him or break him out of jail. -> XP
The people who tried to kill the king have tried to kill the king before. The former captain of the guard was slain in the last attempt, and is now a restless spirit. Help the spirit rest in peace and let him know the party will protect the king in his stead? -> XP
Party is afraid an assassination attempt will be made at the King's country manor, to which a diplomatic meeting has suddenly been moved. Party cases the joint making sure all vulnerabilities in security and inherent in the property are seen to? --> XP
Lots of games (RPGs and Computer games) have rewarded XP for finding peaceful solutions or just generally being a nice guy. Take a look at the walkthroughs for games like "Planescape", Fallout 1 and 2, Icewind dale, Baldur's gate... and you'll find plenty of objectives that can be realized without violence and rewarded (along with many more that are)