Todd... something is REALLY wrong here...
I have a Stant Radiator Cap #28229 (in a box or 18229 on a card) that I bought new about 5 years ago I guess... and a Stant Thermostat #45378.
My system never develops enough pressure to blow through this cap at 13 pounds... and your 25 pound cap was really screwed up. I believe most HIGH pressure systems today are generally 16 - 18 pounds.
Here are some KEY LEARNINGS for ME I wrote about sometime back you may wish to review.
http://www.network54.com/Forum/12159/message/1131515511/THERMOSTAT+102
Also consider this...
At atmosphereic pressure, most coolants (water) boils around 212F degrees and for every SINGLE POUND of pressure you can add to the system... will RAISE the boiling point of water about 3 degrees.
(All Rocket Scientists here can now correct me with true figures... but for the sake of conversation... I'll continue...)
As you are probably aware... most water pumps, including ours, do not pump STEAM or any other gases very well. They are made to circulate LIQUIDS. Coolants flashing to steam inside the system no longer absorb heat and will not circulate... This is BAD!
A properly operating system just short of 13 pounds pressure will keep most coolants in a LIQUID state up to about 251 degrees (212+ [3x13] = 251... which is about where the RED zone is on your guage.
After that, the cap should open and vent the coolant, (which will flash to steam as its now been "superheated") to the ground or a catch can if you have one. Your engine should be having trouble RUNNING at this temperature also...
Anyway... the cap, your cap, being at 25 pounds
or at 13 pounds is NOT the cause of the problem, but simply a contributing EFFECT or FACTOR... At 25 pounds... you could theoretically superheat the coolant to 290 degrees or so and still not blow it off!
Something else is really wrong. Like I said before... if it is heating up FAST, its usually a BLOCKAGE. Like a fan belt coming off, the water temp at speed will raise to 260 within a minute or so from 180. If this is how yours acts... going along fine and then it shoots up... I suspect you have a blockage, or floating blockage. Could be at the radiator also... or in the head from a piece of old gasket, etc.
If I were you, I'd pull the lower radiator hoses or at the stat and pull the stat... and flush, and BACK FLUSH the system and radiator and note if anything comes out... using a garden hose with house pressure, rags and clamps...
Hope this helps...