Hi Megiddo,
The synatax for CEILING is:
CEILING(num-to-round,multiple-factor)
Jerry has provided an example in which the number to be rounded is 4.76, and the multiple factor is 0.05 (ie. to the next nickel). The result is 4.80.
For your use, the number to be rounded is the result of your discount formula, (Retail Prices :: 4x5 Dark Red*0.8)
Substitute that expression for the number 4.76, and you have the formula that will work for you.
One thing that bothers me about CEILING is shown in the table below.
Column B, labeled retail contains the retail prices, all in even dollars.
Column C, labeled discount has your 20% discount applied. As the retail prices here are all even dollar amounts, the discount is a multiple of 20 cents, and the prices, extended to a third decimal place, all end with at least two zeroes.
Column D shows the same calculation, with CEILING applied to the results. Note that for most amounts, CEILING has moved the amount up despite the original calculation having a result that is already a multiple of 0.05. The only exceptions are when the original (retail) price is a power of 2.
In column E, I've added another step, and rounded the result of the discount calculation to two decimal places before applying CEILING. For all the examples (except row 7, where the retail price is $5), this provides what I'd see as a more correct result.

Formulas:
Column C (discounted): =B*0.8
Column D (Ceiling applied): =CEILING(B*0.8,0.05)
Column E (rounded, then CEILING applied): =CEILING(ROUND(B*0.8,2),0.05)
"This is my first numbers project. :-)"
Then the best advice available is to download and spend some time reading the two excellent resources available through the Help menu in Numbers.
The numbers '09 User Guide will give you an overview of the application itself. I'd recommend reading at least the first three chapters, then diipping into the rest when the need arises.
The iWork Formulas and Functions User Guide is a great reference when you're trying to write formulas. It lists all of the functions supported by numbers, with a description of each, suggestions regarding where it is useful, and at least one example for each function.
Regards,
Barry