Character levels in total have a 20 level cap, whether single or multi-classed in standard campaigns. There are very very limited rules for progression beyond 20, but it's a major grind.... essentially it requires a doubling of your exp total for each level.
20 is the max level. It can be 20 levels in one class, or 1 level in 20 classes, but you never go over level 20.
Outside of Mythic are there rules for going beyond 20th?
There's a paragraph about it somewhere in the CRB. That's ALL there is. But I'm sure you're not going to like it. Support for such IS built into Herolab though.
There's a paragraph about it somewhere in the CRB.
Yup, it's here. It's not intended to be used much beyond 20, though...
There have been attempts to go beyond level 20. The small section in the CRB, mythic, and the D&D epic level book have all been mentioned.
The big problem is that the math goes from extreme to predictably wonky. Saving throws, for example, soon become pass/fail no matter what you roll (except for the natural 1, natural 20 caveats). 40th level PCs against a CR41+ threat will find that a full BAB never misses while a half BAB will never hit without natural 1s or 20s. Strong save will never fail an appropriate threat without a natural 1. Weak saves will always fail without a natural 20.
In other words, the farther beyond level 20 you go, the more predictably binary things can get. If your players don't mind that, go for it.
Outside of Mythic are there rules for going beyond 20th?
Mythic isn't meant for going beyond 20 the way epic was. It's designed to pad the 1-20 experience.
The experience chart in the Gamemastering chapter of the CRB goes to 25, funny enough. There's also this section:
Beyond 20th Level
Although Classes doesn't describe what happens after 20th level, this isn't to say that there are no resources available to you should you wish to continue your campaign on to 21st level and beyond. Rules for epic-level play like this exist in numerous products that are compatible with the Pathfinder Roleplaying Game, although in many cases these alternative rules can provide unanticipated problems. For example, if your campaign world is populated by creatures and villains who, at the upper limit of power, can challenge a 20th-level character, where will epic-level PCs go for challenges? You might be looking at creating an entirely new campaign setting, one set on different planes, planets, or dimensions from the one where your players spent their first 20 levels, and that's a lot of work.Paizo Publishing may eventually publish rules to take your game into these epic realms, but if you can't wait and would rather not use existing open content rules for epic-level play, you can use the following brief guidelines to continue beyond 20th level. Note that these guidelines aren't robust enough to keep the game vibrant and interesting on their own for much longer past 20th level, but they should do in a pinch for a campaign that needs, say, 22 or 23 experience levels to wrap up. Likewise, you can use these rules to create super-powerful NPCs for 20th-level characters to face.
Experience Points: To gain a level beyond 20th, a character must double the experience points needed to achieve the previous level. Thus, assuming the medium XP progression, a 20th-level character needs 2,100,000 XP to become 21st level, since he needed 1,050,000 XP to reach 20th level from 19th. He'd then need 4,200,000 XP to reach 22nd level, 8,400,000 XP to reach 23rd, and so on.
Scaling Powers: Hit dice, base attack bonuses, and saving throws continue to increase at the same rate beyond 20th level, as appropriate for the class in question. Note that no character can have more than 4 attacks based on its base attack bonus. Note also that, before long, the difference between good saving throws and poor saving throws becomes awkwardly large—the further you get from 20th level, the more noticeable this difference grows, and for high-level characters, bolstering their poor saving throws should become increasingly important. Class abilities that have a set, increasing rate, such as a barbarian's damage reduction, a fighter's bonus feats and weapon training, a paladin's smite evil, or a rogue's sneak attack continue to progress at the appropriate rate.
Spells: A spellcaster's caster level continues to increase by one for each level beyond 20th level. Every odd-numbered level, a spellcaster gains access to a new level of spell one above his previous maximum level, gaining one spell slot in that new level. These spell slots can be used to prepare or cast spells adjusted by metamagic feats or any known spell of lower levels. Every even-numbered level, a spellcaster gains additional spell slots equal to the highest level spell he can currently cast. He can split these new slots any way he wants among the slots he currently has access to.
For example, a 21st-level wizard gains a single 10th-level spell slot, in which he can prepare any spell of level 1st through 9th, or in which he can prepare a metamagic spell that results in an effective spell level of 10 (such as extended summon monster IX, or quickened disintegrate). At 22nd level he gains 10 spell-levels' worth of new spell slots, and can gain 10 1st-level spells per day, two 5th-level spells per day, one 7th-level and one 3rd-level spell per day, or one more 10th-level spell per day. At 23rd level, he gains a single 11th-level spell slot, and so on.
Spellcasters who have a limited number of spells known (such as bards and sorcerers) can opt out of the benefits they gain (either a new level of spells or a number of spell slots) for that level and in exchange learn two more spells of any level they can currently cast.
You might want to further adjust the rate of spell level gain for classes (like paladins and rangers) who gain spells more slowly than more dedicated spellcaster classes.
Multiclassing/Prestige Classes: The simplest way to progress beyond 20th level is to simply multiclass or take levels in a prestige class, in which case you gain all of the abilities of the new class level normally. This effectively treats 20th level as a hard limit for class level, but not as a hard limit for total character level.
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As another option (which can be combined with Mythic, as well), you can run an "e20" version of Pathfinder: For every 1,500,000/1,000,000/750,000 XP after reaching 20th level (depending on if you're running Slow/Medium/Fast advancement), the character gains a feat (but no actual levels).
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20 is the max level. It can be 20 levels in one class, or 1 level in 20 classes, but you never go over level 20.
But it says here that you can exceed a total of 20 character levels:
Multiclassing/Prestige Classes: The simplest way to progress beyond 20th level is to simply multiclass or take levels in a prestige class, in which case you gain all of the abilities of the new class level normally. This effectively treats 20th level as a hard limit for class level, but not as a hard limit for total character level.