Shoes is so new and in flux that unless you are comfortable cracking open some Ruby code and lots of C you will have a hard time getting started. I made a little cheat sheet of Shoes for the presentation I gave. It is moth eaten and worse yet, half-assed. I apologize in advance, but maybe somebody will find it useful.
The format here is that method names are in bold. An english description of the arguments (I know it is a terrible thing to do) follow, along with a description of what it does.
background - takes a filename or a color created by rgb(r,g,b) followed by an array of :top, :right, :left, :height, :width
rgb - takes 3 parameters 0-254 and returns a color
width - gives you the width of an element
button - takes a String label and a block and draws a button to the screen
show - make an element that is not visible, visible.
alert - takes a String message and pops up an alert box.
title - takes a String and prints out some big text
contents - returns an array of the elements in this Shoes Object.
ask_color - takes a String which is the title of the color selection dialog that pops up
width= - looks like it lets you set width (but it doesn't resize the base window)
rect - Takes a hash :left, :top, :width, :height and draw a rectangle
quit - close the application window
click - I think it takes a block like keypress, but i just get segfaults.
incident - causes your app to segfault
rotate - takes a number of degrees. and rotates things you have drawn.
height - gives you the height of the element.
flow - A style element that takes an array with :margin and a block consisting of other elements to display. Flows fill left to right. When they hit max width they go down to the next row.
gray - takes an integer, but nothing happens.
border - takes a rgb() color and an array of :strokewidth
display - not sure, think it has something to do with debugging messages you see.
list_box - a selection element that takes a hash of :items where items is a list of options.
height= - set the height of the element.
clear - can take a block. clears what was drawn in the block or without a block clears the whole window.
ask_open_file - takes a string which is the title of the file open dialog box.
goto - takes a url string and redirects you to some url.
text - take a string and display it on the screen. Understands html markup.
subtitle - takes a string and displays some larger than normal text.
stack - A style element that takes an array with :margin and a block consisting of other
image - Takes a filename and displays that image.
edit_line - An element that takes text input
nostroke - the things you draw won't have a stroke line.
release
smalltitle - takes a string and displays some largeish, but not too large text.
stroke - i don't know what parameters it takes, i think maybe a stack or flow, but it sets the stroke width on things you draw.
strokewidth - takes a number that becomes the width of the strokes you make
hide - make an element invisible
animate - takes a number representing frames per second and a block that happens that many times per sec.
confirm - takes a string that is the confirmation message for the confirmation dialog that pops up.
progress - show a progress bar. I have no idea how to fill it up.
keypress - takes a block that gets the value from the keypress. pretty much segfaults every time.
If you have the time I really recommend digging into the C code behind shoes. It practically documents itself!