seandeg - I think you have a couple of obstacles to overcome.
First, the macro name is USART_RX_BUF_SIZE and not USART_RX_BUFFER_SIZE.
Second, the usart_dev struct, which contains the USART_RX_BUF_SIZE buffer for each USART, are statically defined in usart.c. So you might be able to persuade the code to use a smaller part of that buffer, but the buffer can't be increased in size unless usart.c is recompiled and linked to your program.
The value of USART_RX_BUF_SIZE could be redefined by defining it, e.g.
#define USART_RX_BUF_SIZE 128
before including uasrt.h. However, if it is to take effect, usart.c needs to be compiled too, with this change. So either usart.h needs to be edited to change the 64 to 128, or usart.c needs the #define added before including usart.h.
I'd probably make a copy of usart.h and usart.c, into the project's directory, edit (at least) one of them, and add usart.c as a tab in the IDE. WARNING: I haven't checked this, it might be that the include path doesn't include the current directory. So you might want to change the #include <...> to #include "..." to ensure the project's copy is the one used.
(Edit: removed error about libmaple)
(Full disclosure: I am not a member of LeafLabs staff)