Very helpful, thank you.
I've had a Canon Rebel xti for just over a week.
		
		
	 
Then I totally understand the enthusiasm  *smile*.  Just a couple of thoughts---since you've just had the camera a short time and I don't know from what other camera you came from, I assume you have read the manual cover to cover--always a good thing.
Then--even though I'm a strong user of PS and have used it since PS3 (and now use LR also), 
1.)  I would recommend you get to know your camera well, learning to use the various creative modes (Av, Tv, M) and why (I know others gave good information in your river blog thread), learning how to use the histo and apply EC (exposure compensation) when needed (and ISO when needed also)--and get the best image possible from the camera.  
2.) From that point--learn how to work with RAW and your chosen RAW converter.  If you have PS (BTW--I don't think we know what version of PS you have which would be helpful when anyone suggests a technique--or esp. in RAW conversion), then you have ACR which is a RAW converter, and if not, you still have DPP (the Canon RAW converter).  Take the RAW file and get the best image BEFORE conversion you can.  
3.) Convert and use PS to do any post work to get that image to match your 'vision' that you weren't able to do in the actual shot and RAW conversion if needed.  And today---with ACR 4.1/2 and /or LR (Lightroom) there are many that feel there's little they have to do after conversion except sharpen for the final output (after resizing if needed), be it web or print--IF they started out with a good exposure and got the best out of that RAW file before conversion to tiff or psd.
Getting that good exposure is easier now than in film days--esp. if the subject is static.  The histogram really IS your best friend LOL.  Understanding metering, the available modes (evaluative, center weighted and spot if the XTi has it--don't know), using EC when needed---all will contribute to a better image in conjunction with reading the histogram.  
Having RAW to work with is wonderful--no more depending upon a lab to develop---you make all the decisions now--and its well worth it to sink your teeth into it and learn it before trying to correct things in PS.  When you work in RAW you are able to tweak without degrading the image--before conversion.
Then--of course its great fun to work in PS--so many options and you've gotten some good advice for masking, layers, etc.  Once you get a handle on layers and masks your 1/2 way home, so to speak LOL.  None of us will ever 'know' all PS, but there's a lot of good info out there.
I won't even touch on things like composition, DOF--any of that which lie in the realm of 'intent' and vision---since its been discussed a good bit in this thread and that's not what I'm addressing.  We all want to get out there and shoot--I'm champing at the bit myself right now, but you'll be so much more at ease with the camera and ready to spend time on composing just the right shot in the VF and how you want that shot to look--if you understand the best way to get that shot and what and how you can make it even better afterwards.  My final thought though---I do better myself in understanding by hands on--so that means shooting---a lot---but also editing and analysis of what worked, what didn't--and why.  We're all here to help, but sometimes it really takes working through some of this yourself as you've mentioned about PS.
One more little thought---I have a huge string of bookmarks that I use to, hopefully, link you to some specific tutorials.  Any time you feel you need some help (ex.---if you want to know just how to actually use a RAW converter--there are tutorials that will take you step by step through them), feel free to ask for some of those URLs.
Good shooting,
Diane